Study of blood collection and sample preparation for analysis of vitamin D and its metabolites by liquid chromatography–tandem mass spectrometry

The analysis of vitamin D status, with special emphasis on 25-hydroxyvitamin D and 1,25-dihydroxyvitamin D, is gaining interest in clinical studies due to the classical and non-classical effects attributed to this prohormone. In this research, the influence of the two steps preceding determination (viz. sample collection and preparation) on the quantitative analysis of vitamin D and its more important metabolites has been studied. Two preparation approaches, deproteination and solid-phase extraction (SPE), have been evaluated in terms of sensitivity to delimit their application, thus establishing that detection of 1,25-dihydroxyvitamin D cannot be addressed by protein precipitation. Concerning sample collection, serum and plasma reported high accuracy (above 83.3%) for vitamin D and metabolites, while precision, expressed as relative standard deviation, was below 12.9% for all analytes in both samples. Statistical analysis revealed that serum and plasma provided similar physiological levels for vitamin D₃, 24,25-dihydroxyvitamin D₃ and 25-hydroxyvitamin D₃, while significantly different levels were obtained for 1,25-dihydroxyvitamin D₃, always higher in plasma than in serum. Sample collection and treatment have proved to be significant in the analysis of vitamin D and its relevant metabolites.     

Enhancing the Water Stability of Al‐MIL‐101‐NH2 via Postsynthetic Modification

The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH₂ by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N₂ and H₂O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m² g^?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with ¹H‐²⁷Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking.     

A stable pillared metal–organic framework constructed by H4TCPP ligand as luminescent sensor for selective detection of TNP and Fe3+ ions

A novel luminescent metal–organic framework ( Zn‐TCPP/BPY ) with pillared structure based on 2,3,5,6‐tetrakis(4‐carboxyphenyl)pyrazine (H₄TCPP) and 4,4′‐bipyridine (BPY) has been designed and synthesized through a solvothermal reaction. The [Zn₂(COO)₄] paddlewheel units are linked by TCPP^4? ligands to form two‐dimensional layers and further connected by BPY ligands as pillars to construct the twofold interpenetrating three‐dimensional framework. Interestingly, Zn‐TCPP/BPY possesses outstanding stability in organic solvents and water as well as maintains its structural rigidity in aqueous solutions of different pH values (3–12). After activation, Zn‐TCPP/BPY possesses permanent porosity with Brunauer–Emmett–Teller surface area of 630 m² g^–1. Remarkably, Zn‐TCPP/BPY displays excellent fluorescent property in virtue of the aggregation‐induced emission effect of the H₄TCPP ligand, which can be highly active and quenched by small amounts of 2,4,6‐trinitrophenol (TNP) and Fe³⁺ ions. Furthermore, the detection effect of Zn‐TCPP/BPY remains basically the same even after five cycles. The excellent stability, high sensitivity, and recyclability of Zn‐TCPP/BPY make it an outstanding chemical sensor for detecting TNP and Fe³⁺ ions.     

Uniform stability of semilinear wave equations with arbitrary local memory effects versus frictional dampings

This paper is concerned with the mixed initial–boundary value problem for semilinear wave equations with complementary frictional dampings and memory effects. We successfully establish uniform exponential and polynomial decay rates for the solutions to this initial–boundary value problem under much weak conditions concerning memory effects. More specifically, we obtain the exponential and polynomial decay rates after removing the fundamental condition that the memory-effect region includes a part of the system boundary, while the condition is a necessity in the previous literature; moreover, for the polynomial decay rates we only assume minimal conditions on the memory kernel function g, without the usual assumption of $g^{\prime }$ controlled by g.     

Modification of an implicit approach based on nonstandard rules for structural dynamics analysis

The present study aims to modify a recently suggested implicit approach consisted of the approximate Euler method and closed-form exponential mapping (herein referred to as the Liu scheme) for the dynamic analysis of structures. Such modification has been developed based upon nonstandard rules. The equation of motion is formulated in the augmented dynamic space to apply the exponential mapping as a group preserving scheme. The formulation of the proposed method involves the hyperbolic sine and cosine functions. The method is therefore prone to divergence due to the behavior of the hyperbolic functions in structures with a high ratio of stiffness to mass. In the present study, to consider the properties of the structural equation into the formulation of the time step size and thereby avoid the divergence, a parameter, known as stability parameter, is thus derived from the exact solution of the equation of motion based on nonstandard rules. Embedding this parameter into the proposed method improves its stability. Afterward, for evaluating the performance of the proposed method, it is applied to several structures with different loading patterns while implemented in programing environment of the Matlab software. The results are compared to those of several commonly used numerical methods in structural applications. It is found that the proposed method has acceptable convergence and accuracy, and low time consumption compared to several commonly used methods. Furthermore, its stability is guaranteed by embedding the stability parameter into the proposed method.     

Mono-Aryl/Alkylthio-Substituted (Hetero)acenes of Exceptional Thermal and Photochemical Stability by the Thio-Friedel–Crafts/Bradsher Cyclization Reaction

The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (T_decomp.=331–354 °C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60–70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio-Friedel–Crafts/Bradsher cyclization reaction of hitherto unknown [o-(1,3-dithian-2-yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono-aryl/alkylthio-substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD-DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono-aryl/alkylthio-substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S₁ state by molecular oxygen.     

Two-dimensional vortex sheets for the nonisentropic Euler equations: Nonlinear stability

We show the short-time existence and nonlinear stability of vortex sheets for the nonisentropic compressible Euler equations in two spatial dimensions, based on the weakly linear stability result of Morando and Trebeschi (2008) [20]. The missing normal derivatives are compensated through the equations of the linearized vorticity and entropy when deriving higher-order energy estimates. The proof of the resolution for this nonlinear problem follows from certain a priori tame estimates on the effective linear problem in the usual Sobolev spaces and a suitable Nash–Moser iteration scheme.     

Periodic Solutions of the Duffing Differential Equation Revisited via the Averaging Theory

We use three different results of the averaging theory of first order for studying the existence of new periodic solutions in the two Duffing differential equations $\ddot y+ a \sin y= b \sin t$ and $\ddot y+a y-c y^3=b\sin t$, where $a$, $b$ and $c$ are real parameters.     

Structure and Mechanical Stability of Epoxy Modified Polyurethane Foam Under Heat and Stress

A series of phenolic epoxy resin (PEP) modified polyurethane foams (PUF) were prepared via an in-situ polymerization, one step process. It was found that the epoxy modified PUF foam exhibited a perforated network structure with larger cell size, higher open cell porosity and enhanced ovality compared with pure PUF. With increasing content of PEP, the tensile strength, elongation at break and low temperature modulus of PUF decreased. A single T_g was observed for PEP modified PUF, indicating that the two component phases of the polyurethane-epoxy were miscible. With increasing PEP content, the T_g of PUF shifted slightly to higher temperature, tan δ_max dropped to lower values, and the retention value of the storage modulus at ?20 and ?10?°C increased. For pure PUF, the cell walls degraded and the structure became disordered after aging under heat and stress, while for PUF/20wt%PEP, the degradation degree was obviously reduced, and an orientation of the cells along the stress direction and a density increase was observed. During aging at 200?°C, the retention of the mechanical properties of PUF/20wt% PEP was much higher than that of pure PUF, and it showed superior stability under heat and stress, attributed to incorporation of the thermally resistant oxazolidone rings and benzene rings in the PU backbones, the highly cross-linked networks of the polyurethane-epoxy systems and the obvious orientation of the cells under stress.     

Distinguishability and Disturbance in the Quantum Key Distribution Protocol Using the Mean Multi-Kings’ Problem

We introduce a quantum key distribution protocol using mean multi-kings’ problem. Using this protocol, a sender can share a bit sequence as a secret key with receivers. We consider a relation between information gain by an eavesdropper and disturbance contained in legitimate users’ information. In BB84 protocol, such relation is known as the so-called information disturbance theorem. We focus on a setting that the sender and two receivers try to share bit sequences and the eavesdropper tries to extract information by interacting legitimate users’ systems and an ancilla system. We derive trade-off inequalities between distinguishability of quantum states corresponding to the bit sequence for the eavesdropper and error probability of the bit sequence shared with the legitimate users. Our inequalities show that eavesdropper’s extracting information regarding the secret keys inevitably induces disturbing the states and increasing the error probability.