Comparison of photodiode array,evaporative light scattering,and single-quadrupole mass spectrometric detection methods for the UPLC analysis of pyrolysis liquids

It is important to analyze pyrolysis liquids to evaluate the yield of valuable products as well as unfavorable by-products. This work focuses on choosing detectors for reversed-phase ultra high-performance liquid chromatography analysis of pyrolysis liquids. The linearity, sensitivity, precision, and recovery of photodiode array (PDA) detector, single-quadrupole mass spectrometer (MS), and evaporative light scattering (ELS) detector were compared for the quantitative determination of several typical compounds found in pyrolysis liquids. PDA and MS detectors were found to be suitable for the quantification of furans and phenol derivatives (furfural, vanillin, syringol), but sugars and their derivatives (glucose, xylose, levoglucosan) can be analyzed with MS or ELS detectors.     

Barriers to Small Molecule Drug Discovery for Systemic Amyloidosis

Inhibition of amyloid fibril formation could benefit patients with systemic amyloidosis. In this group of diseases, deposition of amyloid fibrils derived from normally soluble proteins leads to progressive tissue damage and organ failure. Amyloid formation is a complex process, where several individual steps could be targeted. Several small molecules have been proposed as inhibitors of amyloid formation. However, the exact mechanism of action for a molecule is often not known, which impedes medicinal chemistry efforts to develop more potent molecules. Furthermore, commonly used assays are prone to artifacts that must be controlled for. Here, potential mechanisms by which small molecules could inhibit aggregation of immunoglobulin light-chain dimers, the precursor proteins for amyloid light-chain (AL) amyloidosis, are studied in assays that recapitulate different aspects of amyloidogenesis in vitro. One molecule reduced unfolding-coupled proteolysis of light chains, but no molecules inhibited aggregation of light chains or disrupted pre-formed amyloid fibrils. This work demonstrates the challenges associated with drug development for amyloidosis, but also highlights the potential to combine therapies that target different aspects of amyloidosis.     

Lipase-Catalyzed Production of Sorbitol Laurate in a “2-in-1” Deep Eutectic System: Factors Affecting the Synthesis and Scalability

Surfactants, such as glycolipids, are specialty compounds that can be encountered daily in cleaning agents, pharmaceuticals or even in food. Due to their wide range of applications and, more notably, their presence in hygiene products, the demand is continuously increasing worldwide. The established chemical synthesis of glycolipids presents several disadvantages, such as lack of specificity and selectivity. Moreover, the solubility of polyols, such as sugars or sugar alcohols, in organic solvents is rather low. The enzymatic synthesis of these compounds is, however, possible in nearly water-free media using inexpensive and renewable building blocks. Using lipases, ester formation can be achieved under mild conditions. We propose, herein, a “2-in-1” system that overcomes solubility problems, as a Deep Eutectic System (DES) made of sorbitol and choline chloride replaces either a purely organic or aqueous medium. For the first time, 16 commercially available lipase formulations were compared, and the factors affecting the conversion were investigated to optimize this process, owing to a newly developed High-Performance Liquid Chromatography-Evaporative Light Scattering Detector (HPLC-ELSD) method for quantification. Thus, using 50 g/L of lipase formulation Novozym 435^® at 50 °C, the optimized synthesis of sorbitol laurate (SL) allowed to achieve 28% molar conversion of 0.5 M of vinyl laurate to its sugar alcohol monoester when the DES contained 5 wt.% water. After 48h, the de novo synthesized glycolipid was separated from the media by liquid–liquid extraction, purified by flash-chromatography and characterized thoroughly by one- and two-dimensional Nuclear Magnetic Resonance (NMR) experiments combined to Mass Spectrometry (MS). In completion, we provide initial proof of scalability for this process. Using a 2.5 L stirred tank reactor (STR) allowed a batch production reaching 25 g/L in a highly viscous two-phase system.     

Electronic,bonding, and optical properties of 1d [CuCN]n (n = 1–10) chains, 2d [CuCN]n (n = 2–10) nanorings,and 3d [Cun(CN)n]m (n = 4, m = 2, 3; n = 10, m = 2) tubes studied by DFT/TD‐DFT methods

The electronic, bonding, and photophysical properties of one‐dimensional [CuCN]_n (n = 1–10) chains, 2‐D [CuCN]_n (n = 2–10) nanorings, and 3‐D [Cu_n(CN)_n]_m (n = 4, m = 2, 3; n = 10, m = 2) tubes are investigated by means of a multitude of computational methodologies using density functional theory (DFT) and time‐dependent‐density‐functional theory (TD‐DFT) methods. The calculations revealed that the 2‐D [CuCN]_n (n = 2–10) nanorings are more stable than the respective 1‐D [CuCN]_n (n = 2–10) linear chains. The 2‐D [CuCN]_n (n = 2–10) nanorings are predicted to form 3‐D [Cu_n(CN)_n]_m (n = 4, m = 2, 3; n = 10, m = 2) tubes supported by weak stacking interactions, which are clearly visualized as broad regions in real space by the 3D plots of the reduced density gradient. The bonding mechanism in the 1‐D [CuCN]_n (n = 1–10) chains, 2‐D [CuCN]_n (n = 2–10) nanorings, and 3‐D [Cu_n(CN)_n]_m (n = 4, m = 2, 3; n = 10, m = 2) tubes are easily recognized by a multitude of electronic structure calculation approaches. Particular emphasis was given on the photophysical properties (absorption and emission spectra) of the [CuCN]_n chains, nanorings, and tubes which were simulated by TD‐DFT calculations. The absorption and emission bands in the simulated TD‐DFT absorption and emission spectra have thoroughly been analyzed and assignments of the contributing principal electronic transitions associated to individual excitations have been made. © 2015 Wiley Periodicals, Inc.     

Cd3[B2P4O14(OH)4]: A 3D Open‐Framework Cadmium Borophosphate with Unique Twisted 8‐Ring Channels

Abstract. The cadmium borophosphate compound Cd₃[B₂P₄O₁₄(OH)₄] was synthesized under mild hydrothermal conditions. The crystal structure was determined by single‐crystal X‐ray diffraction [triclinic, space group P$\bar{1}$ (no. 2), a = 5.4362(11) Å, b = 8.2190(16) Å, c = 8.3918(17) Å, and α = 111.87(3)°, β = 104.63(3)°, γ = 90.73(3)°, V = 334.29(12) ų and Z = 1]. The 3D open framework of the title compound is constructed from BO₃(OH) tetrahedra and 2D layers along the [100] direction. The resulting framework contains twisted eight‐membered rings that form 1D channels.     

探讨妊娠糖尿病运用个体化营养膳食的影响

目的了解妊娠期糖尿病专业治疗中行个体化营养膳食疗法对其妊娠结局以及血糖控制水平产生的影响。方法选择130例因妊娠期糖尿病进入江西省萍乡市人民医院的患者,以膳食疗法的差异分组:62例Ⅰ组施以常规膳食疗法,68例Ⅱ组则施以个体化营养膳食疗法,再对两组病例血糖值及其妊娠结局专业统计、观察。结果施以两种膳食疗法后,62例Ⅰ组FPG值(5.60±0.90)mmol/L,68例Ⅱ组(4.47±0.49)mmol/L,(P<0.05);同时Ⅱ组2h PG值及其妊娠结局等都优于Ⅰ组,(P<0.05)。结论对于患有糖尿病的妊娠期患者,通过施以个体化营养膳食疗法,可实现对妊娠结局的充分改善,值得推荐应用。     

Large deviations for generalized Polya urns with arbitrary urn function

We consider a generalized two-color Polya urn (black and white balls) first introduced by Hill et al. (1980), where the urn composition evolves as follows: let $\pi :\left[0,1\right]\to \left[0,1\right]$, and denote by $x_n$ the fraction of black balls after step $n$, then at step $n+1$ a black ball is added with probability $\pi \left(x_n\right)$ and a white ball is added with probability $1?\pi \left(x_n\right)$. Originally introduced to mimic attachment under imperfect information, this model has found applications in many fields, ranging from Market Share modeling to polymer physics and biology.In this work we discuss large deviations for a wide class of continuous urn functions $\pi$. In particular, we prove that this process satisfies a Sample-Path Large Deviations principle, also providing a variational representation for the rate function. Then, we derive a variational representation for the limit

$?\left(s\right)=\underset{n\to \infty }{lim}\frac{1}{n}log\mathbb{P}\left(n{x}_n=?sn?\right),s\in \left[0,1\right],$

where $n{x}_n$ is the number of black balls at time $n$, and use it to give some insight on the shape of $?\left(s\right)$. Under suitable assumptions on $\pi$ we are able to identify the optimal trajectory. We also find a non-linear Cauchy problem for the Cumulant Generating Function and provide an explicit analysis for some selected examples. In particular we discuss the linear case, which embeds the Bagchi–Pal Model [6], giving the exact implicit expression for $?$ in terms of the Cumulant Generating Function.     

From N‐Nitro to N‐Nitroamino: Preparation of High‐Performance Energetic Materials by Introducing Nitrogen‐Containing Ions

In the design of energetic materials, high energetic performance and good molecular stability are two main goals. Energetic functionalization which strives for maximum energy often results in unstable chemical bonds and causes safety problems in practical production and storage operations. In this work, N‐nitro‐ and N‐nitroamino‐functionalized mono‐ and bis(1,2,4‐triazoles) were synthesized and characterized by infrared, and multinuclear NMR spectra, and elemental analyses. The N‐nitroamino‐functionalization strategy was employed for bis(imidazole), leading to high density compound 14 (2.007 g cm^?3 at 100 K; 1.94 g cm^?3 at room temperature) and energetic salt 15 . While N‐nitro‐functionalized products are thermally unstable and highly moisture sensitive, N‐nitroamino‐functionalized energetic salts, which are comprised of additional nitrogen‐containing ions, exhibit good density, moderate to excellent structural stabilities, and high performance.     

Toward the total synthesis of vineomycin B2: application of an efficient glycosylation methodology using 2,3-unsaturated sugars

The application of an efficient glycosylation methodology using 2,3-unsaturated sugars to synthesize critical precursors required for the total synthesis of an antibiotic, vineomycin B₂ (1), was demonstrated. The required disaccharide, the acurosyl rhodinose derivative of 1, was prepared by chemoselective glycosylation using a 2,3-saturated glycosyl acetate corresponding to the rhodinose moiety and a 2,3-unsaturated glycosyl acetate corresponding to the acurose portion. Further, the right-hand side chain of 1, consisting of β-oxo-tert-alcohol and rhodinose, was constructed by a powerful glycosylation approach using a 2,3-unsaturated glycosyl acetate in an ionic liquid under reduced pressure.