Direct Conversion of Sugars and Ethyl Levulinate into γ‑Valerolactone with Superparamagnetic Acid–Base Bifunctional ZrFeO_<i>x</i> Nanocatalysts

Acid–base bifunctional superparamagnetic FeZrO_<i>x</i> nanoparticles were synthesized via a two-step process of solvothermal treatment and hydrolysis–condensation, and were further employed to catalyze the conversion of ethyl levulinate (EL) to γ-valerolactone (GVL) using ethanol as both H-donor and solvent. ZrFeO(1:3)-300 nanoparticles (12.7 nm) with Fe₃O₄ core covered by ZrO₂ layer (0.65 nm thickness) having well-distributed acid–base sites (0.39 vs 0.28 mmol/g), moderate surface area (181 m²/g), pore size (9.8 nm), and strong magnetism (35.4 Am² kg^–1) exhibited superior catalytic performance, giving a high GVL yield of 87.2% at 230 °C in 3 h. The combination of the nanoparticles with solid acid HY2.6 promoted the direct transformation of sugars to produce GVL in moderate yield (around 45%). Moreover, the nanocatalyst was easily recovered by a magnet for six cycles with an average GVL yield of 83.9% from EL

Rapid and efficient conversion of bio-based sugar to 5-hydroxymethylfurfural using amino-acid derived catalysts

<p>A series of low-cost and sustainable amino-acid derived catalysts including glutamic acid hydrochlorate (GluCl), glycine hydrochlorate (GlyCl), alanine hydrochlorate (AlaCl) and valine hydrochlorate (ValCl) were prepared by using a simple assembly method and characterized by ¹H/¹³C NMR (nuclear magnetic resonance) and FT-IR (Fourier transform infrared) techniques. These amino-acid based catalysts were highly efficient for the production of an important platform molecule 5-hydroxymethylfurfural (HMF) from biomass-derived sugars under oil-heating conditions. A high HMF yield of 83.7% at fructose conversion of 99.3% was achieved in merely 15 min at 120ºC. The catalyst could be reused for four times with no significant loss of its catalytic activity.</p

Secondary structure of tRNA families in <i>Peirates</i> mitochondrial genomes.

<p>The nucleotide substitution pattern for each tRNA family is modeled using as reference the structure determined for PF. Red arrows correspond to insertions. The tRNAs are labeled with the abbreviations of their corresponding amino acids. Inferred Watson-Crick bonds are illustrated by lines, whereas GU bonds are illustrated by dots.</p

Analyses of polymorphic sites among <i>Aphis craccivora</i>, <i>Aphis glycines</i> and <i>Aphis gossypii</i>.

<p>Analyses of polymorphic sites among <i>Aphis craccivora</i>, <i>Aphis glycines</i> and <i>Aphis gossypii</i>.</p

Organization of the control region in <i>Peirates</i> mitochondrial genomes.

<p>The colored panes indicate the structural elements in the CR, leading sequences are shown as blue panes, strings of Gs as yellow panes, A+T-rich sequences as purple panes and the remainders of control regions as green panes.</p

The non-synonymous and synonymous nucleotide substitutions calculated for each taxa.

<p>The non-synonymous and synonymous nucleotide substitutions calculated for each taxa.</p

Comparative Mitogenomics of the Assassin Bug Genus <i>Peirates</i> (Hemiptera: Reduviidae: Peiratinae) Reveal Conserved Mitochondrial Genome Organization of <i>P. atromaculatus</i>, <i>P. fulvescens</i> and <i>P. turpis</i>

<div><p>In this study, we sequenced four new mitochondrial genomes and presented comparative mitogenomic analyses of five species in the genus <i>Peirates</i> (Hemiptera: Reduviidae). Mitochondrial genomes of these five assassin bugs had a typical set of 37 genes and retained the ancestral gene arrangement of insects. The A+T content, AT- and GC-skews were similar to the common base composition biases of insect mtDNA. Genomic size ranges from 15,702 bp to 16,314 bp and most of the size variation was due to length and copy number of the repeat unit in the putative control region. All of the control region sequences included large tandem repeats present in two or more copies. Our result revealed similarity in mitochondrial genomes of <i>P. atromaculatus</i>, <i>P. fulvescens</i> and <i>P. turpis</i>, as well as the highly conserved genomic-level characteristics of these three species, e.g., the same start and stop codons of protein-coding genes, conserved secondary structure of tRNAs, identical location and length of non-coding and overlapping regions, and conservation of structural elements and tandem repeat unit in control region. Phylogenetic analyses also supported a close relationship between <i>P. atromaculatus</i>, <i>P. fulvescens</i> and <i>P. turpis</i>, which might be recently diverged species. The present study indicates that mitochondrial genome has important implications on phylogenetics, population genetics and speciation in the genus <i>Peirates</i>.</p></div

Phylogenetic relationships among <i>Peirates</i> assassin bugs inferred from 37 mitochondrial genes.

<p>Phylogram from the Bayesian analysis of partitioned 37 mitochondrial genes is shown. Numbers close to the branching points are bootstrap support values from the ML analysis, bootstrap support values from NJ analysis and posterior probabilities from the Bayesian analysis.</p

Structural feature of <i>Peirates</i> mitochondrial genomes used in this study.

<p>Structural feature of <i>Peirates</i> mitochondrial genomes used in this study.</p

Identifying reprogramming candidates.

<p>For a given cell fate, we plot every differentially expressed transcription factor's (TF) predictivity (aka energy projection-contribution, ) vs TF expression level (z-score normalized). Unless otherwise stated all existing reprogramming protocols to a given cell fate are labeled. (A) Schematic illustrating predictivity vs expression level plots. The large positive (negative) predictivity and large positive (negative) gene expression TFs are candidates for over expression (knock out) in a reprogramming protocol. The TFs with z-score between and are highlighted in gray because <a href="http://www.ploscompbiol.org/article/info:doi/10.1371/journal.pcbi.1003734#pcbi-1003734-g002" target="_blank">Figure 2B</a> suggests these TFs predictivity may be prone to extra noise induced by the data discretization. (B) Embryonic stem cell, ESC (induced pluripotent stem cells, iPSC). Original Takahashi and Yamanaka factors <i>Pou5f1</i> (<i>Oct 4</i>), <i>Sox2</i>, <i>Klf4</i>, and <i>Myc </i><a href="http://www.ploscompbiol.org/article/info:doi/10.1371/journal.pcbi.1003734#pcbi.1003734-Takahashi1" target="_blank">[1]</a>. (C) Inset of ESC positive predictivity and gene expression. <i>Zfp42</i> (<i>Rex1</i>) <a href="http://www.ploscompbiol.org/article/info:doi/10.1371/journal.pcbi.1003734#pcbi.1003734-Masui1" target="_blank">[40]</a> and <i>Nr0b1</i> (<i>Dax1</i>) <a href="http://www.ploscompbiol.org/article/info:doi/10.1371/journal.pcbi.1003734#pcbi.1003734-Khalfallah1" target="_blank">[41]</a> are pluripotency markers that are not necessary to overexpress for reprogramming, while combinations of the remaining labeled TFs have been successfully used in reprogramming protocols <a href="http://www.ploscompbiol.org/article/info:doi/10.1371/journal.pcbi.1003734#pcbi.1003734-Gonzlez1" target="_blank">[8]</a>. (D) Heart (induced cardiomyocytes, iCM) <a href="http://www.ploscompbiol.org/article/info:doi/10.1371/journal.pcbi.1003734#pcbi.1003734-Ieda1" target="_blank">[3]</a>. (E) Liver (induced hepatocytes, iHep). There are two published protocols. One protocol used <i>Hnf4a</i> plus any of <i>Foxa1</i>, <i>Foxa2</i>, or <i>Foxa3 </i><a href="http://www.ploscompbiol.org/article/info:doi/10.1371/journal.pcbi.1003734#pcbi.1003734-Sekiya1" target="_blank">[4]</a> while another used <i>Gata4</i>, <i>Foxa3</i>, <i>Hnf1a</i>, and deletion of <i>p19Arf </i><a href="http://www.ploscompbiol.org/article/info:doi/10.1371/journal.pcbi.1003734#pcbi.1003734-Huang1" target="_blank">[5]</a>. <i>p19Arf</i> was not differentially expressed in our microarrays and is not shown. (F) Thyroid <a href="http://www.ploscompbiol.org/article/info:doi/10.1371/journal.pcbi.1003734#pcbi.1003734-Antonica1" target="_blank">[7]</a>. (G) Neural Progenitor Cells, NPC (induced NPC, iNPC) used <i>Pou3f2</i> (<i>Brn2</i>), <i>Sox2</i>, and <i>Foxg1 </i><a href="http://www.ploscompbiol.org/article/info:doi/10.1371/journal.pcbi.1003734#pcbi.1003734-Lujan1" target="_blank">[6]</a>. With our microarrays we find that <i>Foxg1</i> is not predictive for NPC but is predictive of neural stem cells (NSC) (see <a href="http://www.ploscompbiol.org/article/info:doi/10.1371/journal.pcbi.1003734#pcbi.1003734.s003" target="_blank">Figure S3</a>). (H) Neurons (induced neuron, iN) <a href="http://www.ploscompbiol.org/article/info:doi/10.1371/journal.pcbi.1003734#pcbi.1003734-Vierbuchen1" target="_blank">[2]</a>. The reprogramming protocol used a combination of factors that were known to be important to ether mature neurons (<i>Myt1l</i>) or NPCs (<i>Pou3f2</i>, <i>Ascl1</i>). (G) shows that <i>Pou3f2</i> and <i>Ascl1</i> are predictive of NPCs.</p