Local packing environment strongly influences the frictional properties of mixed CH3- and CF3-terminated alkanethiol SAMs on Au(111)

Compositionally mixed, self-assembled monolayers (SAMs) derived from 16,16,16-trifluorohexadecanethiol and a normal alkanethiol, either hexadecanethiol or pentadecanethiol, were formed on Au(111) substrates. The relative composition of the films was determined using X-ray photoelectron spectroscopy and was found to approximately equal the equimolar composition of the isooctane solution from which they were formed. The frictional properties of the mixed films were measured on the nanometer scale using atomic force microscopy and were observed to decrease when the chain length of the CH(3)-terminated component was shortened by one methylene unit (i.e., when hexadecanethiol was replaced by pentadecanethiol). For comparison, the frictional properties of a mixed-chain-length CH(3)-terminated SAM derived from hexadecanethiol and pentadecanethiol in a 1:1 ratio was also examined. In contrast to the mixed CF(3)/CH(3) system, the latter mixed-chain-length system exhibited relatively higher friction when compared to single-component SAMs derived solely from either hexadecanethiol or pentadecanethiol. For both types of mixed films, the change in frictional properties that occurs as a result of modifying the position of neighboring terminal groups with respect to the surface plane is discussed in terms of the influence of local packing environments on interfacial energy dissipation (friction).     

Extended metal atom chains (EMACs) of five chromium or cobalt atoms: symmetrical or unsymmetrical?

Structural studies of pentachromium and pentacobalt extended metal atom chain (EMAC) systems are presented in which the metal chains are helically wrapped by either the pentadentate dianion tripyridyldiamide (tpda) or its diethyl-substituted analogue bis(4-ethyl-2-pyridylamido)pyridine (etpda). The compound Cr(5)(tpda)(4)(NCS)(2), has alternating long and short Cr-Cr distances, contrary to recent reports that describe it as symmetrical with essentially equally spaced chromium atoms. The linear Cr(5)(10+) chain is composed of two Cr(2)(4+) quadruply bonded units and an isolated high spin Cr(II) unit. The new compounds Cr(5)(etpda)(4)Cl(2), [Cr(5)(etpda)(4)FCl]PF(6), and Co(5)(etpda)(4)(NCS)(2)() employ the etpda ligand as "insulation" around a central pentametal-atom "wire." Compound, like all other oxidized pentachromium compounds, has very disparate alternating short-long-short-long Cr-Cr distances, 2.032(3) A, 2.560(6) A, 1.873(5) A, and 2.509(4) A. Compound shows a nearly uniform spacing of the Co atoms, although the outer Co-Co distances (2.279[4] A) are slightly longer than the inner ones (2.239[4] A).     

Surface-enhanced Raman scattering and enhanced fluorescence of dyes on silver chloride sols

The enhanced fluorescence and enhanced Raman spectra of dye-1555 molecules adsorbed on silver chloride sols are detected for the first time. The enhanced fluorescence is attributed to the double resonance effect proposed by Chew and Wang. The enhanced Raman spectra indirectly support the energy-transfer model of spectral sensitization of dyes, one of two competing mechanisms of spectral sensitization in the photographic process.     

阴离子交换色谱中淋洗液流速对测定灵敏度影响的讨论

研究了阴离子交换色谱法定量分析时淋洗液流速对测定灵敏度影响的规律。使用３种不同型号的阴离子交换柱，详细地研究了３种总离子浓度不同的样品中淋洗液流速对峰高和峰面积的影响。实验表明，若标准溶液和样品溶液中的阴离子总浓度相差较大，将在不同程度上影响分析结果的准确度。初步探讨了上述现象的机理。通过紫外（２１０ｎｍ）和电导检测结果的对比观察，说明灵敏度的变化不完全如文献中提到的由抑制器抑制不足或ＮＯ－２质子化所致。在相同条件下改变柱温后的实验结果表明也不是离子交换过程中离子传质速度比较慢引起离子交换不完全的原因。提出的其它机理假设仍需进一步研究证实。     

Au3-to-Ag3 coordinate-covalent bonding and other supramolecular interactions with covalent bonding strength

An efficient strategy for designing charge-transfer complexes using coinage metal cyclic trinuclear complexes (CTCs) is described herein. Due to opposite quadrupolar electrostatic contributions from metal ions and ligand substituents, [Au(μ-Pz-(i-C₃H₇)₂)]₃·[Ag(μ-Tz-(n-C₃F₇)₂)]₃ (Pz = pyrazolate, Tz = triazolate) has been obtained and its structure verified by single crystal X-ray diffraction – representing the 1^st crystallographically-verified stacked adduct of monovalent coinage metal CTCs. Abundant supramolecular interactions with aggregate covalent bonding strength arise from a combination of M–M′ (Au → Ag), metal–π, π–π interactions and hydrogen bonding in this charge-transfer complex, according to density functional theory analyses, yielding a computed binding energy of 66 kcal mol⁻¹ between the two trimer moieties – a large value for intermolecular interactions between adjacent d¹⁰ centres (nearly doubling the value for a recently-claimed Au(i) → Cu(i) polar-covalent bond: Proc. Natl. Acad. Sci. U.S.A., 2017, 114, E5042) – which becomes 87 kcal mol⁻¹ with benzene stacking. Surprisingly, DFT analysis suggests that: (a) some other literature precedents should have attained a stacked product akin to the one herein, with similar or even higher binding energy; and (b) a high overall intertrimer bonding energy by inferior electrostatic assistance, underscoring genuine orbital overlap between M and M′ frontier molecular orbitals in such polar-covalent M–M′ bonds in this family of molecules. The Au → Ag bonding is reminiscent of classical Werner-type coordinate-covalent bonds such as H₃N: → Ag in [Ag(NH₃)₂]⁺, as demonstrated herein quantitatively. Solid-state and molecular modeling illustrate electron flow from the π-basic gold trimer to the π-acidic silver trimer with augmented contributions from ligand-to-ligand’ (LL′CT) and metal-to-ligand (MLCT) charge transfer.

A stacked Ag₃–Au₃ bonded (66 kcal mol⁻¹) complex obtained crystallographically exhibits charge-transfer characteristics arising from multiple cooperative supramolecular interactions.     

碳载CuTAPP的ESR研究(Ⅱ)

本文利用ESR技术详细研究了室温至150℃范围内CuTAPP在碳表面的行为。提出了铜卟啉在碳表面吸附水膜中的二维扩散机理。对较高温度处理后铜卟啉的ESR也作了简要报道。     

A sequential multiple change-point detection procedure via VIF regression

In this paper, we propose a procedure for detecting multiple change-points in a mean-shift model, where the number of change-points is allowed to increase with the sample size. A theoretic justification for our new method is also given. We first convert the change-point problem into a variable selection problem by partitioning the data sequence into several segments. Then, we apply a modified variance inflation factor regression algorithm to each segment in sequential order. When a segment that is suspected of containing a change-point is found, we use a weighted cumulative sum to test if there is indeed a change-point in this segment. The proposed procedure is implemented in an algorithm which, compared to two popular methods via simulation studies, demonstrates satisfactory performance in terms of accuracy, stability and computation time. Finally, we apply our new algorithm to analyze two real data examples.     

The preparation of porous graphite and its application in lithium ion batteries as anode material

Graphite is the most widely used anode material for lithium ion batteries (LIBs). However, the performance of graphite is limited by its slow charging rates. In this work, porous graphite was successfully prepared by nickel-catalyzed gasification. The existence of the pores and channels in graphite particles can greatly increase the number of sites for Li-ion intercalation-deintercalation in graphite lattice and reduce the Li-ion diffusion distance, which can greatly facilitate the rapid diffusion of lithium ions; meanwhile, the pores and channels can act as buffers for the volume change of the graphite in charging-discharging processes. As a result, the prepared graphite with pores and channels exhibits excellent cycling stability at high rate as anode materials for LIBs. The porous graphite offers better cycling performance than pristine graphite, retaining 81.4 % of its initial reversible capacity after 1500 cycles at 5 C rates. The effective synthesis strategy might open new avenues for the design of high-performance graphite materials. The porous graphite anode material is proposed in applications of high rate charging Li-ion batteries for electric vehicles.     

Decarboxylative Coupling Reaction in ESI(−)-MS/MS of 4-Nitrobenzyl 4-Hydroxybenzoates: Triplet Ion–Neutral Complex-Mediated 4-Nitrobenzyl Transfer

In negative electrospray ionization mass spectrometry of 4-nitrobenzyl 4-hydroxybenzoates, a decarboxylation reaction, which was significantly promoted by the presence of a nitro group on the benzyl group, competed with radical elimination reactions. Density functional theory calculations indicated that decarboxylation of deprotonated 4-nitrobenzyl vanillate occurred via a radical route involving homolytic cleavage of the C_benzyl–O bond to give a triplet ion–neutral complex, followed by decarboxylative coupling.

Open image in new window

Graphical Abstract ?