Chemical Variation and Environmental Influence on Essential Oil of Cinnamomum camphora.

Cinnamomum camphora is a traditional aromatic plant used to produce linalool and borneol flavors in southern China; however, its leaves also contain many other unutilized essential oils. Herein, we report geographic relationships for the yield and compositional diversity of C. camphora essential oils. The essential oils of 974 individual trees from 35 populations in 13 provinces were extracted by hydrodistillation and analyzed qualitatively and quantitatively by gas chromatography-mass spectrometry and gas chromatography-flame ionization detection, respectively. Oil yields ranged from 0.01% to 3.46%, with a significantly positive correlation with latitude and a significantly negative correlation with longitude. In total, 41 compounds were identified, including 15 monoterpenoids, 24 sesquiterpenoids, and two phenylpropanoids. Essential oil compositions varied significantly among individuals and could be categorized into various chemotypes. The six main chemotypes were eucalyptol, nerolidol, camphor, linalool, selina, and mixed types. The other 17 individual plants were chemotypically rare and exhibited high levels of methyl isoeugenol, methyl eugenol, δ-selinene, or borneol. Eucalyptol-type plants had the highest average oil yield of 1.64%, followed in decreasing order by linalool-, camphor-, mixed-, selina-, and nerolidol-type plants. In addition, the five main compounds exhibited a clear geographic gradient. Eucalyptol and linalool showed a significantly positive correlation with latitude, while selina-6-en-4-ol was significantly and negatively correlated with latitude. trans-Nerolidol and selina-6-en-4-ol showed significantly positive correlations with longitude, whereas camphor was significantly and negatively correlated with longitude. Canonical correspondence analysis indicated that environmental factors could strong effect the oil yield and essential oil profile of C. camphora.

Chromosome-level genome assembly and resequencing of camphor tree (Cinnamomum camphora) provides insight into phylogeny and diversification of terpenoid and triglyceride biosynthesis of Cinnamomum.

Cinnamomum species attract attentions owing to their scents, medicinal properties, and ambiguous relationship in the phylogenetic tree. Here, we report a high-quality genome assembly of Cinnamomum camphora, based on which two whole-genome duplication (WGD) events were detected in the C. camphora genome: one was shared with Magnoliales, and the other was unique to Lauraceae. Phylogenetic analyses illustrated that Lauraceae species formed a compact sister clade to the eudicots. We then performed whole-genome resequencing on 24 Cinnamomum species native to China, and the results showed that the topology of Cinnamomum species was not entirely consistent with morphological classification. The rise and molecular basis of chemodiversity in Cinnamomum were also fascinating issues. In this study, six chemotypes were classified and six main terpenoids were identified as major contributors of chemodiversity in C. camphora by the principal component analysis. Through in vitro assays and subcellular localization analyses, we identified two key terpene synthase (TPS) genes (CcTPS16 and CcTPS54), the products of which were characterized to catalyze the biosynthesis of two uppermost volatiles (i.e. 1,8-cineole and (iso)nerolidol), respectively, and meditate the generation of two chemotypes by transcriptional regulation and compartmentalization. Additionally, the pathway of medium-chain triglyceride (MCT) biosynthesis in Lauraceae was investigated for the first time. Synteny analysis suggested that the divergent synthesis of MCT and long-chain triglyceride (LCT) in Lauraceae kernels was probably controlled by specific medium-chain fatty acyl-ACP thioesterase (FatB), type-B lysophosphatidic acid acyltransferase (type-B LPAAT), and diacylglycerol acyltransferase 2b (DGAT 2b) isoforms during co-evolution with retentions or deletions in the genome.

Newly Designed Quinazolinone Derivatives as Novel Tyrosinase Inhibitor: Synthesis, Inhibitory Activity, and Mechanism.

We synthesized a series of quinazolinone derivates as tyrosinase inhibitors and evaluated their inhibition constants. We synthesized 2-(2,6-dimethylhepta-1,5-dien-1-yl)quinazolin-4(3H)-one (Q1) from the natural citral. The concentration, which led to 50% activity loss of Q1, was 103 ± 2 µM (IC50 = 103 ± 2 µM). Furthermore, we considered Q1 to be a mixed-type and reversible tyrosinase inhibitor, and determined the KI and KIS inhibition constants to be 117.07 µM and 423.63 µM, respectively. Our fluorescence experiment revealed that Q1 could interact with the substrates of tyrosine and L-DOPA in addition to tyrosinase. Molecular docking studies showed that the binding of Q1 to tyrosinase was driven by hydrogen bonding and hydrophobicity. Briefly, the current study confirmed a new tyrosinase inhibitor, which is expected to be developed into a novel pigmentation drug.

Distribution of mercury in the combustion products from coal-fired power plants in Guizhou, southwest China.

Method 30B and the Ontario Hydro Method (OHM) were used to sample the mercury in the flue gas discharged from the seven power plants in Guizhou Province, southwest China. In order to investigate the mercury migration and transformation during coal combustion and pollution control process, the contents of mercury in coal samples, bottom ash, fly ash, and gypsum were measured. The mercury in the flue gas released into the atmosphere mainly existed in the form of Hg°. The precipitator shows a superior ability to remove Hgp (particulate mercury) from flue gas. The removal efficiency of Hg2+ by wet flue gas desulfurization (WFGD) was significantly higher than that for the other two forms of mercury. The synergistic removal efficiency of mercury by the air pollution control devices (APCDs) installed in the studied power plants is 66.69-97.56%. The Hg mass balance for the tested seven coal-fired power plants varied from 72.87% to 109.67% during the sampling time. After flue gas flowing through APCDs, most of the mercury in coal was enriched in fly ash and gypsum, with only a small portion released into the atmosphere with the flue gas. The maximum discharge source of Hg for power plants was fly ash and gypsum instead of Hg emitted with flue gas through the chimney into the atmosphere. With the continuous upgrading of APCDs, more and more mercury will be enriched in fly ash and gypsum. Extra attention should be paid to the re-release of mercury from the reutilization of by-products from APCDs. Implications: Method 30B and the Ontario Hydro Method (OHM) were used to test the mercury concentration in the flue gas discharged from seven power plants in Guizhou Province, China. The concentrations of mercury in coal samples, bottom ash, fly ash, and gypsum were also measured. By comparison of the mercury content of different products, we found that the maximum discharge source of Hg for power plants was fly ash and gypsum, instead of Hg emitted with flue gas through the chimney into the atmosphere. With the continuous upgrading of APCDs, more and more mercury will be enriched in fly ash and gypsum. Extra attention should be paid to the re-release of mercury from the reutilization of by-products from APCDs.

Using a facile experimental manipulation to fabricate and tune a polyoxometalate-cholesterol hybrid material.

In this work, we describe how the toluene and DMF addition order influences the gelation behaviors and supramolecular structures of a self-assembled polyoxometalate-cholesterol hybrid. Morphological studies of the dried xerogel samples were performed with transmission electron microscopy and atomic force microscopy, revealing that the order of solvent addition directed the self-assembly of polyoxometalate-cholesterol hybrids toward the formation of organogels with different supramolecular structures. In the case of organogel 1, which was formed by adding DMF dropwise into a hybrid-containing toluene solution, the characteristic organogel morphology contained a three-dimensional fibrous network structure. Meanwhile, organogel 2, which was prepared by adding toluene dropwise into a hybrid-containing DMF solution, had a supramolecular structure made up of short ribbons. Based on these results, a mechanism is proposed to illustrate the distinctly different self-assembly mechanisms of hybrid molecules in the formation of organogels 1 and 2. Importantly, the order of solvent addition plays a central role in the aggregation process. This study provides a rational method for the construction of supramolecular soft materials, and can be extended to other self-assembled systems.

Solvent-mediated gel formation, hierarchical structures, and rheological properties of organogels.

We report the formation of solvent-mediated gels as well as their hierarchical structures and rheological properties. The gelator used is a hybrid with a molecular structure of cholesterol-polyoxometalate-cholesterol, in which the cholesterol dissolves well in toluene and N,N-dimethylformamide (DMF), whereas the polyoxometalate cluster dissolves only in DMF. These solubility differences enable the gelator to form thermally reversible supramolecular organogels by mixing solvents of toluene and DMF when the volume fraction, ftol, of toluene is larger than 85.7 v/v%. We found a V-shaped correlation between the gelation times, tgel and ftol: tgel decreases from 1300 min to 2 min when ftol increases from 85.7 v/v% to 90.0 v/v%. It then increases from 2 min to 5800 min when ftol further increases from 90.0 v/v% to 100.0 v/v%. We observed ribbon-like self-assembled structures in the gels as well as a structural evolution from rigid and straight ribbons to twistable ones from ftol=85.7 v/v% to ftol=100.0 v/v%. These ribbons constitute two three-dimensional (3D) gel networks: one is constructed via physical connection of the rigid and straight ribbon, and the other is built up from ribbons splitting and intertwining. The latter has a better 3D gel network that offers improved rheological properties. Fundamentally, this solvent-mediated approach regulates the balance between solubility and insolubility of this gelator in the mixing solvents. It also provides a new method for the preparation of organogels.

Polyoxometalate-biomolecule conjugates: a new approach to create hybrid drugs for cancer therapeutics.

Some polyoxometalate (POM) clusters have demonstrated attractive anticancer properties. Unfortunately, their cytotoxicity upon normal cell is one of fateful side effects obstructing their further clinic application as inorganic drugs. In this communication, we report a new approach to create hybrid drugs potentially for cancer therapeutics. At first, the POM cluster bioconjugates were created by attaching the bioactive ligands on an amine grafted POM via simple amidation reaction. The cytotoxicity study with breast cancer cells (MCF-7 and MDA-MB-231) and non-cancerous breast epithelial cell (MCF-10A) showed that rationally selected ligands with cancer-cell targeting ability on POM-biomolecule conjugates can impart enhanced anti-tumor activity and selectivity, thus representing a new concept to develop novel POM-biomolecule hybrid drugs with the potential synergistic effect: increased bioactivity and lower side effect.