Quantum Defects as a Toolbox for the Covalent Functionalization of Carbon Nanotubes with Peptides and Proteins

Single‐walled carbon nanotubes (SWCNTs) are a 1D nanomaterial that shows fluorescence in the near‐infrared (NIR, >800 nm). In the past, covalent chemistry was less explored to functionalize SWCNTs as it impairs NIR emission. However, certain sp³ defects (quantum defects) in the carbon lattice have emerged that preserve NIR fluorescence and even introduce a new, red‐shifted emission peak. Here, we report on quantum defects, introduced using light‐driven diazonium chemistry, that serve as anchor points for peptides and proteins. We show that maleimide anchors allow conjugation of cysteine‐containing proteins such as a GFP‐binding nanobody. In addition, an Fmoc‐protected phenylalanine defect serves as a starting point for conjugation of visible fluorophores to create multicolor SWCNTs and in situ peptide synthesis directly on the nanotube. Therefore, these quantum defects are a versatile platform to tailor both the nanotube's photophysical properties as well as their surface chemistry.     

Diffusion of Gold Nanoparticles in Inverse Opals Probed by Heterodyne Dynamic Light Scattering

The diffusive behavior of nanoparticles inside porous materials is attracting a lot of interest in the context of understanding, modeling, and optimization of many technical processes. A very powerful technique for characterizing the diffusive behavior of particles in free media is dynamic light scattering (DLS). The applicability of the method in porous media is considered, however, to be rather difficult due to the presence of multiple sources of scattering. In contrast to most of the previous approaches, the DLS method was applied without ensuring matching refractive indices of solvent and porous matrix in the present study. To test the capabilities of the method, the diffusion of spherical gold nanoparticles within the interconnected, periodic nanopores of inverse opals was analyzed. Despite the complexity of this system, which involves many interfaces and different refractive indices, a clear signal related to the motion of particles inside the porous media was obtained. As expected, the diffusive process inside the porous sample slowed down compared to the particle diffusion in free media. The obtained effective diffusion coefficients were found to be wave vector-dependent. They increased linearly with increasing spatial extension of the probed particle concentration fluctuations. On average, the slowing-down factor measured in this work agrees within combined uncertainties with literature data.

     

Investigation of polynuclear Zr(IV) hydroxide complexes by nanoelectrospray mass-spectrometry combined with XAFS

Polynuclear species of zirconium in acidic aqueous solution are investigated by combining X-ray absorption spectroscopy (XAFS) and nanoelectrospray mass spectrometry (ESI-MS). Species distributions are measured between pH_C 0 and pH_C 3 for [Zr] = 1.5–10 mM. While the monomer remains a minor species, with increasing pH the degree of polymerization increases and the formation of tetramers, pentamers, octamers, and larger polymers is observed. The high resolution of the mass spectrometer permits the unambiguous determination of polynuclear zirconium hydroxide complexes by means of their isotopic patterns. The relative abundances of mononuclear and polynuclear species present simultaneously in solution are measured, even if one of the species contributes only 0.1% of the Zr concentration. For the first time it has been directly observed that the hydrolysis of polynuclear Zr species is a continuous process which leads to charge compensation through the sequential substitution of water molecules by hydroxide ligands until doubly charged polymers dominate at conditions (H⁺ and Zr concentrations) close to the solubility of Zr(OH)₄(am). The invasiveness of the electrospray process was minimized by using very mild declustering conditions, leaving the polynuclear species within a solvent shell of approximately 20 water molecules. Figure Schematic Diagram of Multiplexed Measurement of 9 Anti-Nuclear Antibodies Using the AtheNa Multilyte Assay     

Toward Metathesis Reactions on Vinylphosphaalkenes

Abstract

Attempts to utilize C-ethylenic phosphaalkenes in metathesis reactions are discussed. Unprecedented reactivity is observed where the vinylphosphaalkene undergoes the first step of the catalytic cycle and cross-metathesis with the phenylmethylene moiety of Grubbs 2nd generation catalyst. However, homo-metathesis reaction to form 1,6-diphosphahexa-1,3,5-triene is not observed, presumably due to steric constraints.     

甘油氧化的光谱电化学傅里叶变换衰减全反射谱红外光谱薄膜流动池中硼酸镍层厚度的优化

在碱性甘油电氧化反应中,利用电化学傅里叶变换衰减全反射谱红外光谱法,研究了薄膜流动池中滴注硼酸镍催化剂负载量对玻碳电极性能的影响.连续操作的径向流动池包括一个位于内反射元件上方50μm的钻孔电极,可实现红外光谱分析.这是在确定条件下对电催化剂进行简便和可重复筛选的一个适合的方法,同时还提供了对复杂反应(如甘油氧化)产物选择性的检测.通过对泵送电解液进行更耗时的定量高效液相色谱分析,结果表明,衰减全反射红外光谱法可快速鉴定产物.在层流条件下,水中使用0.1 M甘油和1 M KOH,流速为5μL min-1时,甘油转化率较高.转化率和选择性取决于催化剂的负载量,负载量又决定了催化剂层的厚度和粗糙度.由于在更粗糙的膜中停留时间更长有利于再吸附和C-C键断裂,因此当负载量最高达210μg cm-2时,甘油转化率为73％且甲酸选择性接近80％.当最低负载量为13μg cm-2时,甘油转化率达到63％,甲酸选择性降至60％,相应地,C2物种(如乙醇酸盐)选择性较高,为8％.因此,只有催化剂负载量较低时才能形成几微米厚度范围内的薄膜,此时才适合进行优质催化剂的筛选.     

Total Synthesis of Pulvomycin D

A synthetic route to the pulvomycin class of natural products is presented, which culminated in the first synthesis of a pulvomycin, pulvomycin D. Key elements of the strategy include a pivotal aldol reaction which led to bond formation between the C24-C40 and the C8-C23 fragment. The remaining C1-C7 fragment was attached by a Yamaguchi esterification completing the assembly of the 40 carbon atoms within the main skeleton. Ring closure to the 22-membered lactone ring was achieved in the final stages of the synthesis by a Heck reaction. The completion of the synthesis required the removal of six silyl protecting groups in combination with olefin formation at C26-C27 by a Peterson elimination.     

X-ray diffraction effects from 2H crystals undergoing transformation to the 4H structure by the shear mechanism

The 2H or ABAB… structure may be transformed to the 4H or ABCB… structure if deformation faults occur in a non-random manner. The theory of X-ray diffraction from one-dimensionally disordered crystals undergoing the 2H → 4H structural transformation by the deformation mechanism is developed. For this it is necessary to consider that the faults are not distributed entirely at random but tend to occur in such a manner as to statistically create a 4H structure. The X-ray diffraction effects are predicted.     

Scale dependence of branching in arterial and bronchial trees

Although models of branching in arterial and bronchial trees often predict a dependence of bifurcation parameters on the scale of the bifurcating vessels, direct verification of this dependence by comparison with data is uncommon. We compare measurements of bifurcation parameters of airways and arterial trees of different mammals as a function of scale to general features predicted by theoretical models based on minimization of pumping power and network volume. We find that the size dependence is more complex than existing theories based solely on energy and volume minimization explain, and suggest additional factors that may govern the branching at different scales.