Weighted least-squares in calibration: what difference does it make?

In univariate calibration, an unknown concentration or amount x(0) is estimated from its measured response y(0) by comparison with a calibration data set obtained in the same way for known x values. The calibration function y = f(x) contains parameters obtained from a least-squares (LS) fit of the calibration data. Since minimum-variance estimation requires that the data be weighted inversely as their true variances, any other weighting leads to predictable losses of precision in the calibration parameters and in the estimation of x(0). Incorrect weighting also invalidates the apparent standard errors returned by the LS calibration fit. Both effects are studied using Monte Carlo calculations. For the strongest commonly encountered heteroscedasticity, proportional error (sigma(i) proportional, varianty(i)), neglect of weights yields as much as an order of magnitude precision loss for x(0) in the small x region, but only nominal loss in the calibration mid-range. Use of replicates gives great improvement at small x but can underperform unweighted regression in the mid-to-large x region. Variance function estimation approximates minimum-variance, even though the true variance functions are not well reproduced. A relative error test applied to the calibration data themselves is predisposed to favor 1/y(2) (or 1/x(2)) weighting, even if the data are homoscedastic. This predisposition weakens when replicate measurements are taken and disappears when the test is applied to an independent set of data. The distinction between a priori and a posteriori parameter standard errors is emphasized. Where feasible, the a priori approach permits reliable assignment of weights, application of a chi(2) test, and use of the normal distribution for confidence limits.     

Ion spectroscopy: Where did it come from; where is it now; and where is it going?

The ASMS conference on ion spectroscopy brought together at Asilomar on October 16–20, 2009 a large group of mass spectrometrists working in the area of ion spectroscopy. In this introduction to the field, we provide a brief history, its current state, and where it is going. Ion spectroscopy of intermediate size molecules began with photoelectron spectroscopy in the 1960s, while electronic spectroscopy of ions using the photodissociation “action spectroscopic” mode became active in the next decade. These approaches remained for many years the main source of information about ionization energies, electronic states, and electronic transitions of ions. In recent years, high-resolution laser techniques coupled with pulsed field ionization and sample cooling in molecular beams have provided high precision ionization energies and vibrational frequencies of small to intermediate sized molecules, including a number of radicals. More recently, optical parametric oscillator (OPO) IR lasers and free electron lasers have been developed and employed to record the IR spectra of molecular ions in either molecular beams or ion traps. These results, in combination with theoretical ab initio molecular orbital (MO) methods, are providing unprecedented structural and energetic information about gas-phase ions.     

NHC-catalysed benzoin condensation – is it all down to the Breslow intermediate?

The Breslow catalytic cycle describing the benzoin condensation promoted by N-heterocyclic carbenes (NHC) as proposed in the late 1950s has since then been tried by generations of physical organic chemists. Emphasis has been laid on proofing the existence of an enaminol like structure (Breslow intermediate) that explains the observed umpolung of an otherwise electrophilic aldehyde. The present study is not focusing on spectroscopic elucidation of a thiazolydene based Breslow intermediate but rather tries to clarify if this key-intermediate is indeed directly linked with the product side of the overall reaction. The here presented EPR-spectroscopic and computational data provide a fundamentally different view on how the benzoin condensation may proceed: a radical pair could be identified as a second key-intermediate that is derived from the Breslow-intermediate via an SET process. These results highlight the close relationship to the Cannizarro reaction and oxidative transformations of aldehydes under NHC catalysis.     

二面角动力学分析结合Zn2+的淀粉样蛋白Aβ40和Aβ42的多态性特征

淀粉样蛋白β(Aβ)和金属离子与阿尔茨海默病的发病机理密切相关,金属离子与Aβ的相互作用如何导致Aβ动力学行为的变化是从分子水平上理解金属离子调控Aβ聚集生成具有细胞毒性的寡聚体的关键问题之一.利用二面角动力学分析策略,即结合粗粒度模型分析结合Zn2+的Aβ40(Aβ40-Zn2+)和Aβ42(Aβ42-Zn2+)单个二面角的势能分布,利用二面角主成分分析刻画Aβ40-Zn2+和Aβ42-Zn2+的二维势能面,以及应用马尔科夫模型建立Aβ40-Zn2+和Aβ42-Zn2+构象转变的动态网络.结果表明:Aβ40-Zn2+和Aβ42-Zn2+单个二面角的势能分布具有很大的相似程度,其中由Val24-Gly25-Ser26-Asn27构成的二面角差异最大;Aβ40-Zn2+和Aβ42-Zn2+的势能面均很平坦,反映了结合Zn2+的Aβ构象转变需要克服的能垒较低,不同构象处于动态平衡,呈现多态性的特征;马尔科夫模型进一步揭示了Aβ40-Zn2+和Aβ42-Zn2+构象转变的动态特征,由一定相似程度的构象聚类而成的微观状态均处于折叠网络的中转节点,从动力学上反映了结合Zn2+的Aβ构象转变容易发生.特别的,与实验结果一致,发现β折叠结构在含Zn2+的Aβ构象中作用微小.     

Hydrothermal Synthesis and Characterization of a New Arsenic–Vanadium Compound with a β-[As<Subscript>8</Subscript>V<Subscript>14</Subscript>O<Subscript>42</Subscript>(SO<Subscript>4</Subscript>)]<Superscript>6−</Superscript> anion

A new arsenic vanadium compound (NH₄)₂[N(CH₃)₄]₄[β-As₈V₁₄O₄₂(SO₄)] 1 has been synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction, IR spectrum, elemental analysis and thermogravimetic (TG) analysis. Compound 1 crystallizes in monoclinic system with space group P2(1)/c, a = 11.4631(5) Å, b = 11.3539(5) Å, c = 24.6265(10) Å, β = 93.6620(10)°, V = 3198.6(2) ų, Z = 2, R1 = 0.0421 and wR2 = 0.1044. The molecule structural analysis reveals that compound 1 has a β-[As₈V₁₄O₄₂(SO₄)]^6? arsenic–vanadium cluster anion.     

The Electronic Structure of the Al3− Anion: Is it Aromatic?

Multiconfigurational high‐level electronic structure calculations show that the ${{\rm Al}{{- \hfill \atop 3\hfill}}}$ ring‐like cluster anion has three close low‐lying electronic states of different spin, all of them having strong multiconfigurational character. The aromaticity of the cluster has, therefore, been studied by means of total electron delocalization and normalized multicenter electron delocalization indices evaluated from the multiconfigurational wave functions of each state. The lowest‐lying singlet and triplet states are found to be highly aromatic, whereas the next lowest‐lying state, the quintet state, has much less, though non‐negligible, aromatic character.     

How to make the Cassie wetting state stable?

Wetting of rough hydrophilic and hydrophobic surfaces is discussed. The stability of the Cassie state, with air trapped in relief details under the droplet, is necessary for the design of true superhydrophobic surfaces. The potential barrier separating the Cassie state and the Wenzel state, for which the substrate is completely wetted, is calculated for both hydrophobic and hydrophilic surfaces. When the surface is hydrophobic, the multiscaled roughness of pillars constituting the surface increases the potential barrier separating the Cassie and Wenzel states. When water fills the hydrophilic pore, the energy gain due to the wetting of the pore hydrophilic wall is overcompensated by the energy increase because of the growth of the high-energetic liquid-air interface. The potential barrier separating the Cassie and Wenzel states is calculated for various topographies of surfaces. Structural features of reliefs favoring enhanced hydrophobicity are elucidated.     

Fluorescence of New o‐Carborane Compounds with Different Fluorophores: Can it be Tuned?

Two sets of o‐carborane derivatives incorporating fluorene and anthracene fragments as fluorophore groups have been successfully synthesized and characterized, and their photophysical properties studied. The first set, comprising fluorene‐containing carboranes 6 – 9 , was prepared by catalyzed hydrosilylation reactions of ethynylfluorene with appropriate carboranylsilanes. The compound 1‐[(9,9‐dioctyl‐fluorene‐2‐yl)ethynyl]carborane ( 11 ) was synthesized by the reaction of 9,9‐dioctyl‐2‐ethynylfluorene and decaborane (B₁₀H₁₄). Furthermore, reactions of the lithium salt of 11 with 1 equivalent of 4‐(chloromethyl)styrene or 9‐(chloromethyl)anthracene yielded compounds 12 and 13 . Members of the second set of derivatives, comprising anthracene‐containing carboranes, were synthesized by reactions of monolithium or dilithium salts of 1‐Me‐1,2‐C₂B₁₀H₁₁, 1‐Ph‐1,2‐C₂B₁₀H₁₁, and 1,2‐C₂B₁₀H₁₂ with 1 or 2 equivalents of 9‐(chloromethyl)anthracene, respectively, to produce compounds 14 – 16 . In addition, 2 equivalents of the monolithium salts of 1‐Me‐1,2‐C₂B₁₀H₁₁ (Me‐o‐carborane) and 1‐Ph‐1,2‐C₂B₁₀H₁₁ (Ph‐o‐carborane) were reacted with 9,10‐bis(chloromethyl)anthracene to produce compounds 17 and 18 , respectively. Fluorene derivatives 6 – 9 exhibit moderate fluorescence quantum yields (32–44 %), whereas 11 – 13 , in which the fluorophore is bonded to the C_cluster (C_c), show very low emission intensity (6 %) or complete fluorescence quenching. The anthracenyl derivatives containing the Me‐o‐carborane moiety exhibit notably high fluorescence emissions, with ?_F=82 and 94 %, whereas their Ph‐o‐carborane analogues are not fluorescent at all. For these compounds, we have observed a correlation between the C_c?C_c bond length and the fluorescence intensity in CH₂Cl₂ solution, comparable to that observed for previously reported styrene‐containing carboranes. Thus, our hypothesis is that for systems of this type the fluorescence may be tuned and even predicted by changing the substituent on the adjacent C_c.     

In vitro amyloid Aβ<Subscript>1-42</Subscript> peptide aggregation monitoring by asymmetrical flow field-flow fractionation with multi-angle light scattering detection

Self-assembly of the 42-amino-acid-long amyloid peptide Aβ_1-42 into insoluble fibrillar deposits in the brain is a crucial event in the pathogenesis of Alzheimer's disease. The fibril deposition occurs through an aggregation process during which transient and metastable oligomeric intermediates are intrinsically difficult to be accurately monitored and characterised. In this work, the time-dependent Aβ_1-42 aggregation pattern is studied by asymmetrical flow field-flow fractionation with on-line multi-angle light scattering detection. This technique allows separating and obtaining information on the molar mass (M _r) and size distribution of both the early-forming soluble aggregates and the late prefibrillar and fibrillar species, the latter having very high M _r. Preliminary results demonstrate that unique information on the dynamic aggregation process can be obtained, namely on the M _r and size of the forming aggregates as well as on their formation kinetics. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

SO42−/ZrO2 上异丁烷重构化反应机理的原位核磁共振研究

 采用原位魔角旋转固体核磁共振技术研究了 2-13C-异丁烷在 SO42−/ZrO2 上的重构化反应机理, 考察了反应温度和 H2 气氛对反应的影响. 结果表明, 反应初期, 异丁烷在 SO42−/ZrO2 上的重构化反应以单分子机理为主, 之后向双分子机理转变; 反应温度的升高有利于单分子机理向双分子机理的转变; H2 的存在抑制了异丁烷的重构化反应, 特别对其双分子机理的反应有较强的抑制作用.     

The Keto–Enol Tautomerism of Biliverdin in Bacteriophytochrome: Could it Explain the Bathochromic Shift in the Pfr Form?†

Phytochromes are ubiquitous photoreceptors found in plants, eukaryotic algae, bacteria and fungi. Particularly, when bacteriophytochrome is irradiated with light, a Z‐to‐E (photo)isomerization takes place in the biliverdin chromophore as part of the Pr‐to‐Pfr conversion. This photoisomerization is concomitant with a bathochromic shift in the Q‐band. Based on experimental evidence, we studied a possible keto–enol tautomerization of BV, as an alternative reaction channel after its photoisomerization. In this contribution, the noncatalyzed and water‐assisted reaction pathways for the lactam–lactim interconversion through consecutive keto–enol tautomerization of a model BV species were studied deeply. It was found that in the absence of water molecules, the proton transfer reaction is unable to take place at normal conditions, due to large activation energies, and the endothermic formation of lactim derivatives prevents its occurrence. However, when a water molecule assists the process by catalyzing the proton transfer reaction, the activation free energy lowers considerably. The drastic lowering in the activation energy for the keto–enol tautomerism is due to the stabilization of the water moiety through hydrogen bonds along the reaction coordinate. The absorption spectra were computed for all tautomers. It was found that the UV–visible absorption bands are in reasonable agreement with the experimental data. Our results suggest that although the keto–enol equilibrium is likely favoring the lactam tautomer, the equilibrium could eventually be shifted in favor of the lactim, as it has been reported to occur in the dark reversion mechanism of bathy phytochromes.     

Planar tetracoordinate carbon in CE42− (E = Al–Tl) clusters

The structures and bonding of the CE₄^2?clusters (E = Al, Ga, In, Tl) have been theoretically studied via B3LYP/def2-TZVP computations. Total energies were recalculated at the CCSD(T)/def2-TZVPP//B3LYP/def2-TZVP level in order to corroborate the energy differences. Our computations show that all the CE₄^2?and CE₄Li^?clusters (E = Al, Ga, In,Tl) have a planar tetracoordinate carbon structure. Interestingly, while the most stable form of CAl₄Li^? and CGa₄Li^? is planar with coordination of Li⁺ to an edge of the CE₄^2? fragment, for CIn₄Li^? and CTl₄Li^? the pyramidal structures with C_4v symmetry are the lowest-energy structures.     

Polymer modeling: where has it been and where is it going?

The development of the area of polymer modeling often referred to as molecular modeling has been reviewed from its early beginnings to the present day. Key forces influencing the development include computational power, algorithmic advances and access to computational resources. The desire to apply modeling techniques to predict the properties of increasingly complex polymer-containing systems, taken in conjunction with a number of current limitations discussed in this brief review, is expected to define in part some essential future developments.     

Does metal ion complexation make radical clocks run fast?

Ab initio molecular orbital and density functional calculations at the CBS-RAD(QCISD,B3-LYP) level for Li+ and at B3LYP for Na+, K+, Cu+,and Ag+ reveal that the barrier to ring-closure of the 1-hexen-6-yl ("Delta(5)-hexenyl") radical to the cyclopentylmethyl radical, a so-called radical clock reaction, is decreased very significantly by complexation of the double bond to metal cations. This barrier lowering should occur on complexation with many metal ions, as shown by calculations on all of the monovalent ions listed above. Additional density functional calculations including explicit solvation of the model system complexed to the lithium ion with tetrahydrofuran suggest that the effect found is not limited to the gas phase but may also be significant in experimental radical clock reactions in solution, even for lithium.     

<Superscript>35</Superscript>Cl NQR for the SbCl<Subscript>3</Subscript> complex with aniline,SbCl<Subscript>3</Subscript>·NH<Subscript>2</Subscript>C<Subscript>6</Subscript>H<Subscript>5</Subscript>

The temperature dependence of the ³⁵Cl NQR frequencies and spin-lattice relaxation times has been investigated for a trigonal-bipyramidal vn complex SbCl₃·NH₂C₆H₅. Thermally activated motion of chlorine atoms (pseudorotation) was not revealed in the complex, in contrast to the vπ complexes of SbCl₃ with related molecular structures. The high potential barrier of pseudorotation in the aniline complex is likely to be due to the unusually high nonequivalence of Sb-Cl chemical bonds.     

Ternary Systems LiBr–LiVO<Subscript>3</Subscript>–Li<Subscript>2</Subscript>CrO<Subscript>4</Subscript> and KBr–KVO<Subscript>3</Subscript>–K<Subscript>2</Subscript>CrO<Subscript>4</Subscript>

The binary system KVO₃–K₂CrO₄ and two ternary systems, LiBr–LiVO₃–Li₂CrO₄ and KBr–KVO₃–K₂CrO₄, were studied. In the ternary systems, the compositions and melting points of eutectic alloys were determined by differential thermal analysis: (49.0 mol % LiBr, 5.0 mol % LiVO₃, 46.0 mol % Li₂CrO₄, 400°C) and (17.0 mol % KBr, 78.0 mol % KVO₃, 5.0 mol % K₂CrO₄, 458°C), respectively.     

Zr<Subscript>5</Subscript>Ir<Subscript>2</Subscript>In<Subscript>4</Subscript> – A Superstructure of the Lu<Subscript>5</Subscript>Ni<Subscript>2</Subscript>In<Subscript>4</Subscript> Type

Summary. Zr₅Ir₂In₄ was synthesized by reaction of the elements in a glassy carbon crucible in a water-cooled sample chamber of an induction furnace. The sample was characterized by X-ray diffraction on both powder and single crystals. Zr₅Ir₂In₄ crystallizes with a pronounced Lu₅Ni₂In₄ type subcell, space group Pbam, a=1739.5(6), b=766.3(2), c=338.9(2) pm. Weak additional reflections force a doubling of the subcell c axis. The superstructure of Zr₅Ir₂In₄ is of a new type: Pnma, a=1739.5(6), b=677.8(2), c=766.3(2) pm, wR2=0.0529, 1592 F² values, and 60 variable parameters. The group-subgroup scheme for the klassengleiche symmetry reduction is presented. The formation of the superstructure is most likely due to a puckering effect (size of the iridium atoms). The crystal chemistry of Zr₅Ir₂In₄ is briefly discussed.