Biosynthesis of Hybrid Neutral Lipids with Archaeal and Eukaryotic Characteristics in Engineered Saccharomyces cerevisiae

Discovery of the Asgard superphylum of archaea provides new evidence supporting the two-domain model of life: eukaryotes originated from an Asgard-related archaeon that engulfed a bacterial endosymbiont. However, how eukaryotes acquired bacterial-like membrane lipids with a sn-glycerol-3-phosphate (G3P) backbone instead of the archaeal-like sn-glycerol-1-phosphate (G1P) backbone remains unknown. In this study, we reconstituted archaeal lipid production in Saccharomyces cerevisiae by expressing unsaturated archaeol-synthesizing enzymes. Using Golden Gate cloning for pathway assembly, modular gene replacement was performed, revealing the potential biosynthesis of both G1P- and G3P-based unsaturated archaeol by uncultured Asgard archaea. Unexpectedly, hybrid neutral lipids containing both archaeal isoprenoids and eukaryotic fatty acids were observed in recombinant S. cerevisiae. The ability of yeast and archaeal diacylglycerol acyltransferases to synthesize such hybrid lipids was demonstrated.     

Electrocatalytic Hydrogen Evolution by Water-Soluble Cobalt (II), Copper (II) and Iron (III) meso-Tetrakis(carboxyl)porphyrin

Three water-soluble carboxyl metalloporphyrins, cobalt (II), copper (II) and iron (III) meso-tetrakis (carboxyl) porphyrin were prepared and applied as homogeneous electrocatalysts for hydrogen evolution reaction (HER) with acetic acid, trifluoroacetic acid, p-toluene sulfonic acid and water as proton sources. Cyclic voltammetry (CV) results revealed the HER underwent different routes for these metalloporphyrins. Electrocatalysis tests in buffer solution of pH=7.0 showed the TOFs of cobalt (II), copper (II) and iron (III) meso-tetrakis (carboxyl) porphyrin were 184.78, 160.28 and 184.87 mol⁻¹ ⋅ h⁻¹ and the faradaic efficiency were 94.37 %, 93.01 % and 96.98 % at an overpotential of 788 mV, respectively. These results indicate the synthesized metal carboxyl porphyrins have good electrocatalytic activity for HER.     

π-hole bonding: A new retention mechanism for the solid phase extraction of polycyclic aromatic hydrocarbons from the hexane extracts of soil samples

In this work, the perfluorobenzene-bonded silica sorbent was tested to adsorb polycyclic aromatic hydrocarbons in hexane. In the comparison experiments, the perfluorobenzene-bonded sorbent's performance was better than octadecyl silica sorbent and phenyl-bonded silica sorbents, which indicated that the π-hole···π bonds between perfluorobenzene and the polycyclic aromatic hydrocarbons were stronger than π···π interactions and hydrophobic interactions in hexane. Then the perfluorobenzene-bonded silica sorbent was applied to solid-phase extraction of 15 polycyclic aromatic hydrocarbons from the hexane extracts of soil samples directly without the solvent replacement, which simplified the soil pretreatment process. And the results showed that under the optimal conditions, the proposed method for the determination of polycyclic aromatic hydrocarbons in the environment soil presented good recoveries and stabilities for the 10 heavier polycyclic aromatic hydrocarbons with the recoveries ranging from 75.1% to 104.6% and the relative standard deviations being in the range of 1.4%–5.8%. The limits of detection of the method varied from 0.1 to 2 ng/g. This work reveals the great application potential of the π-hole bond as a new retention mechanism in the field of solid-phase extraction.     

A simple and low-energy strategy for the separation of water and acetonitrile

As acetonitrile is a widely used solvent for the chemical industry, the recovery of acetonitrile from acetonitrile wastewater is significant for both industrial cost reduction and environmental protection. In this article, a simple, low-energy, and low-cost strategy is proposed for the effective separation of acetonitrile from high-concentration acetonitrile wastewater. The approach is based on a sequential combination of two steps: salt-induced phase separation and hydrophobic filtration. The acetonitrile wastewater was first induced to split into two phases by salt, that is, the acetonitrile-rich phase and the water-rich phase, then the above two phases were poured into the hydrophobic filter paper funnel for the separation. It was shown that NaCl is a suitable salting-out reagent, and that hydrophobic filter papers—obtained from modification by butyltrichlorosilane and octyltrichlorosilane were the optimal choice for hydrophobic filtration. The salt-induced phase separation process is able to increase the volume fraction of acetonitrile in the acetonitrile-rich phase up to 92%. The acetonitrile-rich phase can pass through the hydrophobic filter paper, whereas the water-rich phase was intercepted. The hydrophobic filter paper retained strong hydrophobicity and high acetonitrile-separating capacity after 3 months storage, or upon immersion in acetonitrile-water mixtures for 12 h, or applied for 25 consecutive separations.     

Pd催化糠醛加氢反应中溶剂依赖效应的理论计算

糠醛催化加氢反应工艺主要分为气相、液相以及催化转移加氢等.相比于糠醛气相加氢,液相加氢为反应提供了更多的可持续性和自由度,但其中溶剂依赖现象对糠醛定向催化转化的影响机制尚不清晰.针对上述问题,本文选用3种溶剂(甲醇、水和环己烷)为研究对象,采用密度泛函方法,从理论计算角度探究了Pd催化糠醛加氢反应中溶剂效应对反应活性和选择性的重要作用.结果表明,在糠醛加氢反应过程中,溶剂一方面能够形成氢键网络促进质子穿梭,另一方面能够稳定反应物、中间体以及生成物,有效降低C=O加氢的能垒.自由能计算结果表明,在液态水、甲醇和环己烷中,随着溶剂极性的降低(水>甲醇>环己烷),第一步C=O氢化的能垒逐渐降低(0.70 eV>0.68 eV>0.44 eV).在水和甲醇介导的糠醛加氢反应过程中,第一步C=O加氢的反应势垒进一步降低为0.47和0.41 eV.差分电荷密度以及Bader电荷分析表明,反应过程中存在糠醛和Pd催化剂之间的电荷转移.分波态密度(PDOS)分析表明,溶剂的加入使d带中心向靠近费米能级的方向移动,表明Pd催化剂的催化活性得到提高.     

Restrained ion population transfer: a novel ion transfer method for mass spectrometry

Fourier transform ion cyclotron resonance (FTICR) mass spectrometers function such that the ion accumulation event takes place in a region of higher pressure outside the magnetic field which allows ions to be thermally cooled before being accelerated toward the ICR cell where they are decelerated and re-trapped. This transfer process suffers from mass discrimination due to time-of-flight effects. Also, trapping ions with substantial axial kinetic energy can decrease the performance of the FTICR instrument compared with the analysis of thermally cooled ions located at the trap center. Therefore, it is desirable to limit the energy imparted to the ions which results in lower applied trap plate potentials and reduces the spread in axial kinetic energy. The approach presented here for ion transfer, called restrained ion population transfer or RIPT, is designed to provide complete axial and radial containment of an ion population throughout the entire transfer process from the accumulation region to the ICR cell, eliminating mass discrimination associated with time-of-flight separation. This was accomplished by use of a number of quadrupole segments arranged in series with independent control of the direct current (DC) bias voltage applied to each segment of the quadrupole ion guide. The DC bias voltage is applied in such a way as to minimize the energy imparted to the ions allowing transfer of ions with low kinetic energy from the ion accumulation region to the ICR cell. Initial FTICR mass spectral data are presented that illustrate the feasibility of RIPT. A larger m/z range for a mixture of peptides is demonstrated compared with gated trapping. The increase in ion transfer time (3 ms to 130 ms) resulted in an approximately 11% decrease in the duty cycle; however this can be improved by simultaneously transferring multiple ion populations with RIPT. The technique was also modeled with SIMION 7.0 and simulation results that support our feasibility studies of the ion transfer process are presented.     

溴代二羟基硝基二苯醚类化合物的合成与抑菌活性研究

综合考虑二苯醚类杀菌剂结构与活性关系的前期研究结果, 以双羟基二苯醚为原料, 经酸酐保护、硝化、去保护得到含硝基的双羟基二苯醚, 再经过溴代反应合成了7个新的溴代2,2'-, 2,4'-和4,4'-二羟基硝基二苯醚; 所有这些化合物的结构均经¹H NMR, MS, IR和元素分析所证实; 并检测了合成的溴代二羟基硝基二苯醚化合物对两种有害菌的抑菌活性, 结果表明: 它们对所测试菌种具有优良的抑制效果, 其中3个化合物在质量分数为5×10^－6的浓度下抑菌率超过100%, 能完全控制细菌的生长.     

New algorithm in the basin hopping Monte Carlo to find the global minimum structure of unary and binary metallic nanoclusters

The basin-hopping Monte Carlo algorithm was modified to more effectively determine a global minimum structure in pure and binary metallic nanoclusters. For a pure metallic Ag55 nanocluster, the newly developed quadratic basin-hopping Monte Carlo algorithm is 3.8 times more efficient than the standard basin-hopping Monte Carlo algorithm. For a bimetallic Ag42Pd13 nanocluster, the new algorithm succeeds in finding the global minimum structure by 18.3% even though the standard basin-hopping Monte Carlo algorithm fails to achieve it.     

Purine and pyrimidine derivatives from the South China Sea gorgonian Subergorgia suberosa

Three new purine derivatives, namely, 4-caryboxy-5,6-dihydro-4H,8H-pyrimido[1,2,3-cd]purine-8,10(9H)-dione (1), 7,9-dihydro-1-(3-oxobutyl)-1H-purine-6,8-dione (2), and 7-hydro-9-(3-oxobutyl)-1H-purine-6,8-dione (3) together with six known purine and pyrimidine derivatives were isolated from the EtOH/CH(2)Cl(2) extracts of the South China Sea gorgonian Subergorgia suberosa. The structures of 1-3 were determined on the bases of extensive spectroscopic analysis, including 1D and 2D NMR data.     

Synthesis and Evaluation of Optical 2‐Benzyl‐5‐bromo‐4‐oxopentanoic Acids as Transition‐state Analog Inhibitors against Carboxypeptidase A

Both enantiomers of 2‐benzyl‐5‐bromo‐4‐oxopentanoic acid were prepared utilizing the diazo ketones as the key intermediates. The compounds were assayed for inhibitory activity against carboxypeptidase A (CPA, EC 3.4.17.1). The (R)‐form is 260‐fold more potent than the corresponding (S)‐form. The finding that (R)‐form, which belongs to the L‐series, is mostly responsible for the inhibitory activity accords with the substrate specificity of CPA. For comparison, both the optical forms of 2‐benzyl‐4‐oxopentanoic acid were also synthesized and evaluated as the inhibitors against CPA. These results reveal that the introduction of a bromo group at the α‐position of ketones can significantly enhance the electrophilicity of the carbonyl group. Further molecular docking study suggested that the gem‐diol form of the α‐bromo ketone, which mimics the transition state in the CPA catalytic process, could chelate the zinc ion in the active site of CPA and thus result in the strong inhibition.