Research Highlights: Focus on Chemistry

Here are a selection of papers rated highly during the review process. This focus of this post is on chemistry and biochemistry, taking in ultra-fast dynamics, testosterone deficiency, a novel bioactive compound from a deep-water sponge, hydrogen storage, and a suggestion for extracting something useful from a large pile of manure.

molecules-logoUltrafast Electronic Deactivation Dynamics of Xanthosine Monophosphate

Katharina Röttger, Rebecca Stellmacher, Mayra C. Stuhldreier and Friedrich Temps

Ultrafast energy dissipation is a crucial factor for the photostability of DNA and RNA, but even some of the key electronic deactivation pathways in monomeric nucleic acid building stones are still controversial. Here, we report on the excited-state dynamics of the rare nucleotide xanthosine monophosphate as a function of deprotonation state (XMP vs. XMP − ) and excitation wavelength ( λpump= 278–243 nm) by femtosecond time-resolved fluorescence and absorption spectroscopy. We show that the predominating relaxation channel leads to a return of the photo-excited molecules to the electronic ground state in τ∼1 ps. The mechanism likely involves an out-of-plane deformation of the five-membered ring, different from the main electronic deactivation pathways in the canonical purine bases adenine and guanine. The results are discussed in terms of the structural and electronic differences of XMP compared to the canonical nucleotides.

IJMS-webTestosterone Deficiency Induces Changes of the Transcriptomes of Visceral Adipose Tissue in Miniature Pigs Fed a High-Fat and High-Cholesterol Diet

Lifan Zhang, Yueqin Cai, Shengjuan Wei, Yun Ling, Liang Zhu, Dongfeng Li and Zhaowei Cai

Testosterone deficiency causes fat deposition, particularly in visceral fat, and its replacement might reverse fat accumulation, however, the underlying mechanisms of such processes under diet-induced adiposity are largely unknown. To gain insights into the genome-wide role of androgen on visceral adipose tissue (VAT), RNA-Seq was used to investigate testosterone deficiency induced changes of VAT in miniature pigs fed a high-fat and high-cholesterol (HFC) diet among intact male pigs (IM), castrated male pigs (CM), and castrated male pigs with testosterone replacement (CMT) treatments. The results showed that testosterone deficiency significantly increased VAT deposition and serum leptin concentrations. Moreover, a total of 1732 differentially expressed genes (DEGs) were identified between any two groups. Compared with gene expression profiles in IM and CMT pigs, upregulated genes in CM pigs, i.e., LOC100520753 (CD68), LCN2, EMR1, S100A9, NCF1 (p47phox), and LEP, were mainly involved in inflammatory response, oxidation-reduction process, and lipid metabolic process, while downregulated genes in CM pigs, i.e., ABHD5, SPP1, and GAS6, were focused on cell differentiation and cell adhesion. Taken together, our study demonstrates that testosterone deficiency alters the expression of numerous genes involved in key biological processes of VAT accumulation under HFC diet and provides a novel genome-wide view on the role of androgen on VAT deposition under HFC diet, thus improving our understanding of the molecular mechanisms involved in VAT changes induced by testosterone deficiency.


marinedrugs-logoDragmacidin G, a Bioactive Bis-Indole Alkaloid from a Deep-Water Sponge of the Genus Spongosorites

Amy E. Wright, K. Brian Killday, Debopam Chakrabarti, Esther A. Guzmán, Dedra Harmody, Peter J. McCarthy, Tara Pitts, Shirley A. Pomponi, John K. Reed, Bracken F. Roberts, Carolina Rodrigues Felix and Kyle H. Rohde

A deep-water sponge of the genus Spongosorites has yielded a bis-indole alkaloid which we have named dragmacidin G. Dragmacidin G was first reported by us in the patent literature and has recently been reported by Hitora et al. from a sponge of the genus Lipastrotheya. Dragmacidin G is the first in this series of compounds to have a pyrazine ring linking the two indole rings. It also has a rare N-(2-mercaptoethyl)-guanidine side chain. Dragmacidin G shows a broad spectrum of biological activity including inhibition of methicillin-resistant Staphylococcus aureus, Mycobacterium tuberculosis, Plasmodium falciparum, and a panel of pancreatic cancer cell lines.


Metals_webImproved Dehydrogenation Properties of 2LiNH2-MgH2 by Doping with Li3AlH6

Shujun Qiu, Xingyu Ma, Errui Wang, Hailiang Chu, Yongjin Zou, Cuili Xiang, Fen Xu and Lixian Sun

Doping with additives in a Li-Mg-N-H system has been regarded as one of the most effective methods of improving hydrogen storage properties. In this paper, we prepared Li3AlH6 and evaluated its effect on the dehydrogenation properties of 2LiNH2-MgH2. Our studies show that doping with Li3AlH6 could effectively lower the dehydrogenation temperatures and increase the hydrogen content of 2LiNH2-MgH2. For example, 2LiNH2-MgH2-0.1Li3AlH6 can desorb 6.43 wt % of hydrogen upon heating to 300 °C, with the onset dehydrogenation temperature at 78 °C. Isothermal dehydrogenation testing indicated that 2LiNH2-MgH2-0.1Li3AlH6 had superior dehydrogenation kinetics at low temperature. Moreover, the release of byproduct NH3 was successfully suppressed. Measurement of the thermal diffusivity suggests that the enhanced dehydrogenation properties may be ascribed to the fact that doping with Li3AlH6 could improve the heat transfer for solid–solid reaction.

agriculture-logoCan Phosphate Salts Recovered from Manure Replace Conventional Phosphate Fertilizer?

Andrea Ehmann, Inga-Mareike Bach, Sukhanes Laopeamthong, Jennifer Bilbao and Iris Lewandowski

Pig farming produces more manure than can reasonably be spread onto surrounding fields, particularly in regions with high livestock densities and limited land availability. Nutrient recycling offers an attractive solution for dealing with manure excesses and is one main objective of the European commission-funded project “BioEcoSIM”. Phosphate salts (“P-Salt”) were recovered from the separated liquid manure fraction. The solid fraction was dried and carbonized to biochar. This study compared the fertilizing performance of P-Salt and conventional phosphate fertilizer and determined whether additional biochar application further increased biomass yields. The fertilizers and biochar were tested in pot experiments with spring barley and faba beans using two nutrient-poor soils. The crops were fertilized with P-Salt at three levels and biochar in two concentrations. Biomass yield was determined after six weeks. Plant and soil samples were analysed for nitrogen, phosphorus and potassium contents. The P-Salt had similar or even better effects than mineral fertilizer on growth in both crops and soils. Slow release of nutrients can prevent leaching, rendering P-Salt a particularly suitable fertilizer for light sandy soils. Biochar can enhance its fertilizing effect, but the underlying mechanisms need further investigation. These novel products are concluded to be promising candidates for efficient fertilization strategies.