bluuebunny/crossref_metadata_2025 huggingface dataset:
Immobilization of Potentially Toxic Elements (PTE) by Mineral-Based Amendments: Remediation of Contaminated Soils in Post-Industrial Sites
Authors: Radziemska Maja , Bęś Agnieszka , Gusiatin Zygmunt M. , Majewski Grzegorz , Mazur Zbigniew , Bilgin Ayla , Jaskulska Iwona , Brtnický Martin
Published: January 2020

In many post-industrial sites, the high contents and high mobility of different potentially toxic elements (PTEs) make the soils unsuitable for effective management and use. Therefore, immobilization of PTE seems to be the best remediation option for such areas. In the present study, soil samples were collected in post-industrial areas in Northeastern Poland. The analyzed soil was characterized by especially high contents of Cd (22 mg·kg−1), Pb (13 540 mg·kg−1), and Zn (8433 mg·kg−1). Yellow lupine (Lupinus luteus L.) and two types of mineral-based amendments were used to determine their combined remediation effect on PTE immobilization. A greenhouse pot experiment was conducted to evaluate the influence of chalcedonite and halloysite on plant growth, chlorophyll a fluorescence, the leaf greenness index (SPAD), PTE uptake, and the physicochemical properties and toxicity of soil. The application of chalcedonite resulted in the greatest increase in soil pH, whereas halloysite contributed to the greatest reduction in the contents of Ni, Pb, Zn, and Cr in soil, compared with the control treatment. The addition of halloysite significantly increased plant biomass. The application of mineral-based amendments increased the ratio of variable fluorescence to maximum chlorophyll fluorescence (Fv/Fm) in yellow lupine leaves. The leaf greenness index was highest in plants growing in soil amended with chalcedonite. The results of this study suggest that mineral-based amendments combined with yellow lupine could potentially be used for aided phytostabilization of multi-PTE contaminated soil in a post-industrial area.
Near-Infrared Spectroscopic Study of Heavy-Metal-Contaminated Loess Soils in Tongguan Gold Area, Central China
Authors: Yang Min , Xu Youning , Zhang Jianghua , Chen Huaqing , Liu San , Li Weiliang , Hao Ying
Published: January 2020

Loess soil is a kind of widespread soil type in northwest China. Human engineering activities such as mining have caused numerous problems related to heavy metal pollution in soils, which threaten people’s health. The band formation mechanism of the near-infrared (NIR) spectral features in loess soils forms the theoretical basis for the study of the soil environment by hyperspectral remote sensing. Some NIR features of loess soils will shift because of the variations of the soil composition and microstructure after they adsorb heavy metal cations. In this study, we focused on the heavy metal adsorption of the illite, smectite, and illite–smectite (I/S) mixed layer in loess soils; evaluated the pollution by Nemerow indexing; applied X-ray diffraction (XRD), mid-infrared (MIR) spectral analysis, and inductively coupled plasma mass spectrometry (ICP-MS); and carefully observed the shift behavior of the MIR and NIR features. Then, the NIR bands were assigned to MIR bands according to the vibration behavior. Furthermore, the relationships between the NIR band positions and the six heavy metal cations as well as the Nemerow index were investigated via multiregression and simple linear correlation methods. Finally, the relationship obtained from the experiments was analyzed using the physical and chemical mechanisms of the heavy metal cations in the clay minerals. These findings may benefit the application of NIR and remote sensing techniques for detecting heavy-metal-polluted soils.
Influence of the Sampling Density in the Coestimation Error of a Regionalized Locally Stationary Variable
Authors: Hernandez Guerra Heber , Alberdi Elisabete , Goti Aitor
Published: January 2020

In the present study, the influence of the sampling density on the coestimation error of a regionalized, locally stationary and geo-mining nature variable is analyzed. The case study is two-dimensional (2D) and synthetic-type, and it has been generated using a non-conditional Sequential Gaussian Simulation (SGS), with subsequent transformation to Gaussian distribution, seeking to emulate the structural behavior of the aforementioned variable. A primary and an auxiliary variable with different spatial and statistical properties are constructed using the same methodology. The collocated ordinary cokriging method has been applied, in which the auxiliary variable is spatially correlated with the primary one and it is known exhaustively. Fifteen sampling densities are extracted from the target population of the primary variable, which are compared with the simulated values after performing coestimation. The obtained results follow a potential function that indicates the mean global error (MGE) based on the sampling density percentage (SDP) ( M G E = 1.2366 · S D P − 0.224 ).
Local-Basis-Function Equation of State for Ice VII–X to 450 GPa at 300 K
Authors: Brown J. Michael , Journaux Baptiste
Published: January 2020

Helmholtz energy of ice VII–X is determined in a pressure regime extending to 450 GPa at 300 K using local-basis-functions in the form of b-splines. The new representation for the equation of state is embedded in a physics-based inverse theory framework of parameter estimation. Selected pressures as a function of volume from 14 prior experimental studies and two theoretical studies constrain the behavior of Helmholtz energy. Separately measured bulk moduli, not used to construct the representation, are accurately replicated below about 20 GPa and above 60 GPa. In the intermediate range of pressure, the experimentally determined moduli are larger and have greater scatter than values predicted using the Helmholtz representation. Although systematic error in the determination of elastic moduli is possible and likely, the alternative hypothesis is a slow relaxation time associated with changes in proton mobility or the ice VII to X transition. A correlation is observed between anomalies in the pressure derivative of the predicted bulk modulus and previously suggested higher-order phase transitions. Improved determinations of elastic properties at high pressure would allow refinement of the current equation of state. More generally, the current method of data assimilation is broadly applicable to other materials in high-pressure studies and for investigations of planetary interiors.
Fluorluanshiweiite, KLiAl1.5□0.5(Si3.5Al0.5)O10F2, a New Mineral of the Mica Group from the Nanyangshan LCT Pegmatite Deposit, North Qinling Orogen, China
Authors: Qu Kai , Sima Xianzhang , Li Guowu , Fan Guang , Shen Ganfu , Liu Xing , Xiao Zhibin , Guo Hu , Qiu Linfei , Wang Yanjuan
Published: January 2020

A new mineral species of the mica group, fluorluanshiweiite, ideally KLiAl1.5□0.5(Si3.5Al0.5)O10F2, has been found in the Nanyangshan LCT (Li, Cs, Ta) pegmatite deposit in North Qinling Orogen (NQO), central China. Fluorluanshiweiite can be regarded as the F-dominant analogue at the A site of luanshiweiite or the K-dominant analogue at the I site of voloshinite. It appears mostly in cookeite as a flaky residue, replaced by Cs-rich mica, or in the form of scale aggregates. Most individual grains are <1 mm in size, with the largest being ca. 1 cm, and the periphery is replaced by cookeite. No twinning is observed. The mineral is silvery white as a hand specimen, and in a thin section, it appears grayish-white to colorless, transparent with white streaks, with vitreous luster and pearliness on cleavage faces. It is flexible with micaceous fracture; the Mohs hardness is approximately 3; the cleavage is perfect on {001}; and no parting is observed. The measured and calculated densities are 2.94(3) and 2.898 g/cm3, respectively. Optically, fluorluanshiweiite is biaxial (–), with α = 1.554(1), β = 1.581(1), γ = 1.583(1) (white light), 2V(meas.) = 25° to 35°, 2V(calc.) = 30.05°. The calculated compatibility index based on the empirical formula is −0.014 (superior). An electron microprobe analysis yields the empirical formula calculated based on 10 O atoms and 2 additional anions of (K0.85Rb0.12Cs0.02Na0.03)Σ1.02[Li1.05Al1.44(□0.47Fe0.01Mn0.02)Σ0.5] Σ2.99(Si3.55Al0.45) Σ4O10F2, which can be simplified to KLiAl1.5□0.5(Si3.5Al0.5)O10F2. Fluorluanshiweiite is monoclinic with the space group C2/m and unit cell parameters a = 5.2030(5), b = 8.9894(6), c = 10.1253(9) Å, β = 100.68(1)°, and V = 465.37(7) Å3. The strongest eight lines in the X-ray diffraction data are [d in Å(I)(hkl)]: 8.427(25) (001), 4.519(57) (020), 4.121(25) (021), 3.628(61) (112), 3.350(60) (022), 3.091(46) (112), 2.586(100) (130), and 1.506(45) (312).
Divergent Asymmetric Total Synthesis of All Four Pestalotin Diastereomers from (R)-Glycidol
Authors: Moriyama Mizuki , Nakata Kohei , Fujiwara Tetsuya , Tanabe Yoo
Published: January 2020

All four chiral pestalotin diastereomers were synthesized in a straightforward and divergent manner from common (R)-glycidol. Catalytic asymmetric Mukaiyama aldol reactions of readily-available bis(TMSO)diene (Chan’s diene) with (S)-2-benzyloxyhexanal derived from (R)-glycidol produced a syn-aldol adduct with high diastereoselectivity and enantioselectivity using a Ti(iOPr)4/(S)-BINOL/LiCl catalyst. Diastereoselective Mukaiyama aldol reactions mediated by catalytic achiral Lewis acids directly produced not only a (1′S,6S)-pyrone precursor via the syn-aldol adduct using TiCl4, but also (1′S,6R)-pyrone precursor via the antialdol adduct using ZrCl4, in a stereocomplementary manner. A Hetero-Diels-Alder reaction of similarly available mono(TMSO)diene (Brassard’s diene) with (S)-2-benzyloxyhexanal produced the (1′S,6S)-pyrone precursor promoted by Eu(fod)3 and the (1′S,6R)-pyrone precursor Et2AlCl. Debenzylation of the (1′S,6S)-precursor and the (1′S,6R)-precursor furnished natural (−)-pestalotin (99% ee, 7 steps) and unnatural (+)-epipestalotin (99% ee, 7 steps), respectively. Mitsunobu inversions of the obtained (−)-pestalotin and (+)-epipestalotin successfully produced the unnatural (+)-pestalotin (99% ee, 9 steps) and (−)-epipestalotin (99% ee, 9 steps), respectively, in a divergent manner. All four of the obtained chiral pestalotin diastereomers possessed high chemical and optical purities (optical rotations, 1H-NMR, 13C-NMR, and HPLC measurements).
γ-Tocotrienol and α-Tocopherol Ether Acetate Enhance Docetaxel Activity in Drug-Resistant Prostate Cancer Cells
Authors: Asay Spencer , Graham Andrew , Hollingsworth Sydney , Barnes Bradley , Oblad Richard V. , Michaelis David J. , Kenealey Jason D.
Published: January 2020

Prostate cancer is the second most commonly diagnosed cancer in men, and metastatic prostate cancer is currently incurable. Prostate cancer frequently becomes resistant to standard of care treatments, and the administration of chemotherapeutic drugs is often accompanied by toxic side effects. Combination therapy is one tool that can be used to combat therapeutic resistance and drug toxicity. Vitamin E (VE) compounds and analogs have been proposed as potential non-toxic chemotherapeutics. Here we modeled combination therapy using mixture design response surface methodology (MDRSM), a statistical technique designed to optimize mixture compositions, to determine whether combinations of three chemotherapeutic agents: γ-tocotrienol (γ-T3), α-tocopherol ether acetate (α-TEA), and docetaxel (DOC), would prove more effective than docetaxel alone in the treatment of human prostate cancer cells. Response surfaces were generated for cell viability, and the optimal treatment combination for reducing cell viability was calculated. We found that a combination of 20 µM γ-T3, 30 µM α-TEA, and 25 nm DOC was most effective in the treatment of PC-3 cells. We also found that the combination of γ-T3 and α-TEA with DOC decreased the amount of DOC required to reduce cell viability in PC-3 cells and ameliorated therapeutic resistance in DOC-resistant PC-3 cells.
Biodegradability of Dental Care Antimicrobial Agents Chlorhexidine and Octenidine by Ligninolytic Fungi
Authors: Linhartová Lucie , Michalíková Klára , Šrédlová Kamila , Cajthaml Tomáš
Published: January 2020

Chlorhexidine (CHX) and octenidine (OCT), antimicrobial compounds used in oral care products (toothpastes and mouthwashes), were recently revealed to interfere with human sex hormone receptor pathways. Experiments employing model organisms—white-rot fungi Irpex lacteus and Pleurotus ostreatus—were carried out in order to investigate the biodegradability of these endocrine-disrupting compounds and the capability of the fungi and their extracellular enzyme apparatuses to biodegrade CHX and OCT. Up to 70% ± 6% of CHX was eliminated in comparison with a heat-killed control after 21 days of in vivo incubation. An additional in vitro experiment confirmed manganese-dependent peroxidase and laccase are partially responsible for the removal of CHX. Up to 48% ± 7% of OCT was removed in the same in vivo experiment, but the strong sorption of OCT on fungal biomass prevented a clear evaluation of the involvement of the fungi or extracellular enzymes. On the other hand, metabolites indicating the enzymatic transformation of both CHX and OCT were detected and their chemical structures were proposed by means of liquid chromatography–mass spectrometry. Complete biodegradation by the ligninolytic fungi was not achieved for any of the studied analytes, which emphasizes their recalcitrant character with low possibility to be removed from the environment.
The Synthesis of α-Aminophosphonates via Enantioselective Organocatalytic Reaction of 1-(N-Acylamino)alkylphosphonium Salts with Dimethyl Phosphite
Authors: Walęcka-Kurczyk Alicja , Walczak Krzysztof , Kuźnik Anna , Stecko Sebastian , Październiok-Holewa Agnieszka
Published: January 2020

α-Aminophosphonic acids are phosphorus analogues of α-amino acids. Compounds of this type find numerous applications in medicine and crop protection due to their unique biological activities. A crucial factor in these activities is the configuration of the stereoisomers. Only a few methods of stereoselective transformation of α-amino acids into their phosphorus analogues are known so far and all of them are based on asymmetric induction, thus involving the use of a chiral substrate. In contrast, we have focused our efforts on the development of an effective method for this type of transformation using a racemic mixture of starting N-protected α-amino acids and a chiral catalyst. Herein, a simple and efficient stereoselective organocatalytic α-amidoalkylation of dimethyl phosphite by 1-(N-acylamino)alkyltriphenylphosphonium salts to enantiomerically enriched α-aminophosphonates is reported. Using 5 mol% of chiral quinine- or hydroquinine-derived quaternary ammonium salts provides final products in very good yields up to 98% and with up to 92% ee. The starting phosphonium salts were easily obtained from α-amino acid derivatives by decarboxylative methoxylation and subsequent substitution with triphenylphosphonium tetrafluoroborate. The appropriate self-disproportionation of enantiomers (SDE) test for selected α-aminophosphonate derivatives via achiral flash chromatography was performed to confirm the reliability of the enantioselectivity results that were obtained.
Profiling the Structural Determinants of Aryl Benzamide Derivatives as Negative Allosteric Modulators of mGluR5 by In Silico Study
Authors: Zhao Yujing , Chen Jiabin , Liu Qilei , Li Yan
Published: January 2020

Glutamate plays a crucial role in the treatment of depression by interacting with the metabotropic glutamate receptor subtype 5 (mGluR5), whose negative allosteric modulators (NAMs) are thus promising antidepressants. At present, to explore the structural features of 106 newly synthesized aryl benzamide series molecules as mGluR5 NAMs, a set of ligand-based three-dimensional quantitative structure-activity relationship (3D-QSAR) analyses were firstly carried out applying comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) methods. In addition, receptor-based analysis, namely molecular docking and molecular dynamics (MD) simulations, were performed to further elucidate the binding modes of mGluR5 NAMs. As a result, the optimal CoMSIA model obtained shows that cross-validated correlation coefficient Q2 = 0.70, non-cross-validated correlation coefficient R2ncv = 0.89, predicted correlation coefficient R2pre = 0.87. Moreover, we found that aryl benzamide series molecules bind as mGluR5 NAMs at Site 1, which consists of amino acids Pro655, Tyr659, Ile625, Ile651, Ile944, Ser658, Ser654, Ser969, Ser965, Ala970, Ala973, Trp945, Phe948, Pro903, Asn907, Val966, Leu904, and Met962. This site is the same as that of other types of NAMs; mGluR5 NAMs are stabilized in the “linear” and “arc” configurations mainly through the H-bonds interactions, π–π stacking interaction with Trp945, and hydrophobic contacts. We hope that the models and information obtained will help understand the interaction mechanism of NAMs and design and optimize NAMs as new types of antidepressants.
Characterization of Volatile and Flavonoid Composition of Different Cuts of Dried Onion (Allium cepa L.) by HS-SPME-GC-MS, HS-SPME-GC×GC-TOF and HPLC-DAD
Authors: Cecchi Lorenzo , Ieri Francesca , Vignolini Pamela , Mulinacci Nadia , Romani Annalisa
Published: January 2020

Onion is widely used worldwide in various forms for both food and medicinal applications, thanks to its high content of phytonutrients, such as flavonoids and volatile sulfur compounds. Fresh onion is very perishable and drying is widely applied for extending shelf-life, thus obtaining a very easy-to-use functional food ingredient. The flavonoid and volatile fractions of different onion cuts (flakes, rings) prepared through different drying cycles in a static oven, were characterized by high-performance liquid chromatography with a diode-array detector HPLC-DAD, Head Space-Solid Phase Micro Extraction followed by Gas Chromatography coupled with Mass Spectrometry (HS-SPME-GC-MS) and Head-Space Solid Phase Micro Extraction followed by comprehensive two-dimensional Gas-Chromatography (HS-SPME-GC×GC-TOF). Onion flakes showed a significantly higher flavonoid content (3.56 mg g−1) than onion rings (2.04 mg g−1). Onion flakes showed greater amount of volatile organic compounds (VOCs) (127.26 mg g−1) than onion rings (42.79 mg g−1), with different relative amounts of di- and trisulfides—disulfides largely predominate the volatile fraction (amounts over 60% on the total volatile content), followed by trisulfides and dipropyl disulfide and dipropyl trisulfide were the most abundant VOCs. HS-SPME-GC×GC-TOF allowed for the detection of the presence of allylthiol, diethanol sulfide, 4,6-diethyl1,2,3,5-tetrathiolane, not detected by HS-SPME-GC-MS, and provided a fast and direct visualization and comparison of different samples. These results highlight different nutraceutical properties of dried onion samples processed otherwise, only differing in shape and size, thus pointing out potentially different uses as functional ingredients.
Constituents from the Seeds of Sophora Alopecuroides L.
Authors: Rong Zi-Jian , Hu Gao-Sheng , Lin Shi-Yi , Yan Ting , Li Na , Zhao Yue , Jia Jing-Ming , Wang An-Hua
Published: January 2020

Three new isoflavone glucosides, kudonol A−C (1–3), two new ester derivatives of phenylpropanoid, kudolignan A and B (4–5) and five known compounds, (−)-maackiain (6), neoliquiritin (7), methyl 4-coumarate (8), methyl ferulate (9) and (+)-wikstromol (10), were isolated from an extract of dried seeds of the traditional Chinese medicinal plant Sophora alopecuroides L. Their structures were established by NMR and HRESIMS data analyses. The monosaccharide part’s configuration of isoflavone glucosides was confirmed by acid hydrolysis and analyzed by a JAsco OR-4090 chiral detector, comparing it to standard substance D-glucose. The cytotoxicity effects against HeLa, Hep3B, MCF-7 and H1299 cells were tested by CCK-8 assay.
Changes in Cuticle Components and Morphology of ‘Satsuma’ Mandarin (Citrus unshiu) during Ambient Storage and Their Potential Role on Penicillium digitatum Infection
Authors: Ding Shenghua , Zhang Jing , Yang Lvzhu , Wang Xinyu , Fu Fuhua , Wang Rongrong , Zhang Qun , Shan Yang
Published: January 2020

To elucidate the role of fruit cuticle in fungal infection, changes in cuticle composition and morphology of ‘Satsuma’ mandarin during ambient (at 25 °C) storage and their role in Penicillium digitatum infection were investigated. Results showed that the epicuticular wax yield increased from 1.11 μg cm−2 to 4.21 μg cm−2 during storage for 20 days and then decreased to 1.35 μg cm−2 as storage time prolonged to 40 days. Intracuticular wax content of fruits stored for 20 days showed a peak value that was 1.7-fold higher than that of fruits stored for 40 days. The contents of cutin monomers of fruits showed a decreased trend during storage, while their proportions in the cutin stayed stable. Acids were identified as the most abundant components in epicuticular wax independently of the storage time, followed by alkanes and terpenoids. Terpenoids were found as the predominant components in intracuticular wax during the whole storage, followed by alkanes and acids. The flattened platelets crystals of fruits at harvest changed into small granule-like wax ones after 10 days of storage then gradually distributed across the surface of the fruits as stored for 40 days. Results of in vitro tests showed that mycelial growth of Penicillium digitatum could be promoted by epicuticular wax and conidial germination could be inhibited by cutin at different storage stages. These results shed new light on the chemical basis for cuticle involvement in fungal infection.
The Pictet-Spengler Reaction Updates Its Habits
Authors: Calcaterra Andrea , Mangiardi Laura , Delle Monache Giuliano , Quaglio Deborah , Balducci Silvia , Berardozzi Simone , Iazzetti Antonia , Franzini Roberta , Botta Bruno , Ghirga Francesca
Published: January 2020

The Pictet-Spengler reaction (P-S) is one of the most direct, efficient, and variable synthetic method for the construction of privileged pharmacophores such as tetrahydro-isoquinolines (THIQs), tetrahydro-β-carbolines (THBCs), and polyheterocyclic frameworks. In the lustro (five-year period) following its centenary birthday, the P-S reaction did not exit the stage but it came up again on limelight with new features. This review focuses on the interesting results achieved in this period (2011–2015), analyzing the versatility of this reaction. Classic P-S was reported in the total synthesis of complex alkaloids, in combination with chiral catalysts as well as for the generation of libraries of compounds in medicinal chemistry. The P-S has been used also in tandem reactions, with the sequences including ring closing metathesis, isomerization, Michael addition, and Gold- or Brønsted acid-catalyzed N-acyliminium cyclization. Moreover, the combination of P-S reaction with Ugi multicomponent reaction has been exploited for the construction of highly complex polycyclic architectures in few steps and high yields. The P-S reaction has also been successfully employed in solid-phase synthesis, affording products with different structures, including peptidomimetics, synthetic heterocycles, and natural compounds. Finally, the enzymatic version of P-S has been reported for biosynthesis, biotransformations, and bioconjugations.
Allosteric Cannabinoid Receptor 1 (CB1) Ligands Reduce Ocular Pain and Inflammation
Authors: Thapa Dinesh , Cairns Elizabeth A. , Szczesniak Anna-Maria , Kulkarni Pushkar M. , Straiker Alex J. , Thakur Ganesh A. , Kelly Melanie E. M.
Published: January 2020

Cannabinoid receptor 1 (CB1) activation has been reported to reduce transient receptor potential cation channel subfamily V member 1 (TRPV1)-induced inflammatory responses and is anti-nociceptive and anti-inflammatory in corneal injury. We examined whether allosteric ligands, can modulate CB1 signaling to reduce pain and inflammation in corneal hyperalgesia. Corneal hyperalgesia was generated by chemical cauterization of cornea in wildtype and CB2 knockout (CB2−/−) mice. The novel racemic CB1 allosteric ligand GAT211 and its enantiomers GAT228 and GAT229 were examined alone or in combination with the orthosteric CB1 agonist Δ8-tetrahydrocannabinol (Δ8-THC). Pain responses were assessed following capsaicin (1 µM) stimulation of injured corneas at 6 h post-cauterization. Corneal neutrophil infiltration was also analyzed. GAT228, but not GAT229 or GAT211, reduced pain scores in response to capsaicin stimulation. Combination treatments of 0.5% GAT229 or 1% GAT211 with subthreshold Δ8-THC (0.4%) significantly reduced pain scores following capsaicin stimulation. The anti-nociceptive effects of both GAT229 and GAT228 were blocked with CB1 antagonist AM251, but remained unaffected in CB2−/− mice. Two percent GAT228, or the combination of 0.2% Δ8-THC with 0.5% GAT229 also significantly reduced corneal inflammation. CB1 allosteric ligands could offer a novel approach for treating corneal pain and inflammation.
Mapping the Photochemistry of European Mid-Latitudes Rivers: An Assessment of Their Ability to Photodegrade Contaminants
Authors: Carena Luca , Vione Davide
Published: January 2020

The abiotic photochemical reactions that take place naturally in sunlit surface waters can degrade many contaminants that pose concern to water bodies for their potentially toxic and long-term effects. This works aims at assessing the ability of European rivers to photoproduce reactive transient intermediates, such as HO• radicals and the excited triplet states of chromophoric dissolved organic matter (3CDOM*), involved in pollutant degradation. A photochemical mapping of the steady-state concentrations of these transients was carried out by means of a suitable modeling tool, in the latitude belt between 40 and 50°N. Such a map allowed for the prediction of the photochemical lifetimes of the phenylurea herbicide isoproturon (mostly undergoing photodegradation upon reaction with HO• and especially 3CDOM*) across different European countries. For some rivers, a more extensive dataset was available spanning the years 1990–2002, which allowed for the computation of the steady-state concentration of the carbonate radicals (CO3•−). With these data, it was possible to assess the time trends of the photochemical half-lives of further contaminants (atrazine, ibuprofen, carbamazepine, and clofibric acid). The calculated lifetimes were in the range of days to weeks, which might or might not allow for efficient depollution depending on the river-water flow velocity.
Synergistic Approach of Ultrafast Spectroscopy and Molecular Simulations in the Characterization of Intramolecular Charge Transfer in Push-Pull Molecules
Authors: Patrizi Barbara , Cozza Concetta , Pietropaolo Adriana , Foggi Paolo , Siciliani de Cumis Mario
Published: January 2020

The comprehensive characterization of Intramolecular Charge Transfer (ICT) stemming in push-pull molecules with a delocalized π-system of electrons is noteworthy for a bespoke design of organic materials, spanning widespread applications from photovoltaics to nanomedicine imaging devices. Photo-induced ICT is characterized by structural reorganizations, which allows the molecule to adapt to the new electronic density distribution. Herein, we discuss recent photophysical advances combined with recent progresses in the computational chemistry of photoactive molecular ensembles. We focus the discussion on femtosecond Transient Absorption Spectroscopy (TAS) enabling us to follow the transition from a Locally Excited (LE) state to the ICT and to understand how the environment polarity influences radiative and non-radiative decay mechanisms. In many cases, the charge transfer transition is accompanied by structural rearrangements, such as the twisting or molecule planarization. The possibility of an accurate prediction of the charge-transfer occurring in complex molecules and molecular materials represents an enormous advantage in guiding new molecular and materials design. We briefly report on recent advances in ultrafast multidimensional spectroscopy, in particular, Two-Dimensional Electronic Spectroscopy (2DES), in unraveling the ICT nature of push-pull molecular systems. A theoretical description at the atomistic level of photo-induced molecular transitions can predict with reasonable accuracy the properties of photoactive molecules. In this framework, the review includes a discussion on the advances from simulation and modeling, which have provided, over the years, significant information on photoexcitation, emission, charge-transport, and decay pathways. Density Functional Theory (DFT) coupled with the Time-Dependent (TD) framework can describe electronic properties and dynamics for a limited system size. More recently, Machine Learning (ML) or deep learning approaches, as well as free-energy simulations containing excited state potentials, can speed up the calculations with transferable accuracy to more complex molecules with extended system size. A perspective on combining ultrafast spectroscopy with molecular simulations is foreseen for optimizing the design of photoactive compounds with tunable properties.
In Situ Construction of CNT/CuS Hybrids and Their Application in Photodegradation for Removing Organic Dyes
Authors: Wang Yanping , Jiang Fuchuan , Chen Jiafu , Sun Xiaofeng , Xian Tao , Yang Hua
Published: January 2020

Herein, a coprecipitation method used to synthesize CuS nanostructures is reported. By varying the reaction time and temperature, the evolution of the CuS morphology between nanoparticles and nanoflakes was investigated. It was found that CuS easily crystallizes into sphere-/ellipsoid-like nanoparticles within a short reaction time (0.5 h) or at a high reaction temperature (120 °C), whereas CuS nanoflakes are readily formed at a low reaction temperature (20 °C) for a long time (12 h). Photodegradation experiments demonstrate that CuS nanoflakes exhibit a higher photodegradation performance than CuS nanoparticles for removing rhodamine B (RhB) from aqueous solution under simulated sunlight irradiation. Carbon nanotubes (CNTs) were further used to modify the photodegradation performance of a CuS photocatalyst. To achieve this aim, CNTs and CuS were integrated to form CNT/CuS hybrid composites via an in situ coprecipitation method. In the in situ constructed CNT/CuS composites, CuS is preferably formed as nanoparticles, but cannot be crystallized into nanoflakes. Compared to bare CuS, the CNT/CuS composites manifest an obviously enhanced photodegradation of RhB; notably, the 3% CNT/CuS composite with CNT content of 3% showed the highest photodegradation performance (η = 89.4% for 120 min reaction, kapp = 0.01782 min−1). To make a comparison, CuS nanoflakes and CNTs were mechanically mixed in absolute alcohol and then dried to obtain the 3% CNT/CuS-MD composite. It was observed that the 3% CNT/CuS-MD composite exhibited a slightly higher photodegradation performance (η = 92.4%, kapp = 0.0208 min−1) than the 3% CNT/CuS composite, which may be attributed to the fact that CuS maintains the morphology of nanoflakes in the 3% CNT/CuS-MD composite. The underlying enhanced photocatalytic mechanism of the CNT/CuS composites was systematically investigated and discussed.
Ablation in Externally Applied Electric and Magnetic Fields
Authors: Maksimovic Jovan , Ng Soon-Hock , Katkus Tomas , An Le Nguyen Hoai , Chon James W.M. , Cowie Bruce C.C. , Yang Tao , Bellouard Yves , Juodkazis Saulius
Published: January 2020

To harness light-matter interactions at the nano-/micro-scale, better tools for control must be developed. Here, it is shown that by applying an external electric and/or magnetic field, ablation of Si and glass under ultra-short (sub-1 ps) laser pulse irradiation can be controlled via the Lorentz force F = e E + e [ v × B ] , where v is velocity of charge e, E is the applied electrical bias and B is the magnetic flux density. The external electric E-field was applied during laser ablation using suspended micro-electrodes above a glass substrate with an air gap for the incident laser beam. The counter-facing Al-electrodes on Si surface were used to study debris formation patterns on Si. Debris was deposited preferentially towards the negative electrode in the case of glass and Si ablation. Also, an external magnetic field was applied during laser ablation of Si in different geometries and is shown to affect ripple formation. Chemical analysis of ablated areas with and without a magnetic field showed strong chemical differences, revealed by synchrotron near-edge X-ray absorption fine structure (NEXAFS) measurements. Harnessing the vectorial nature of the Lorentz force widens application potential of surface modifications and debris formation in external E-/B-fields, with potential applications in mass and charge spectroscopes.
Performance Enhancement of Ultra-Thin Nanowire Array Solar Cells by Bottom Reflectivity Engineering
Authors: Yan Xin , Liu Haoran , Sibirev Nickolay , Zhang Xia , Ren Xiaomin
Published: January 2020

A bottom-reflectivity-enhanced ultra-thin nanowire array solar cell is proposed and studied by 3D optoelectronic simulations. By inserting a small-index MgF2 layer between the polymer and substrate, the absorption is significantly improved over a broad wavelength range due to the strong reabsorption of light reflected at the polymer/MgF2 interface. With a 5 nm-thick MgF2 layer, the GaAs nanowire array solar cell with a height of 0.4–1 μm yields a remarkable conversion efficiency ranging from 14% to 15.6%, significantly higher than conventional structures with a much larger height. Moreover, by inserting the MgF2 layer between the substrate and a part of the nanowire, in addition to between the substrate and polymer, the absorption of substrate right below the nanowire is further suppressed, leading to an optimal efficiency of 15.9%, 18%, and 5.4% for 1 μm-high GaAs, InP, and Si nanowire solar cells, respectively. This work provides a simple and universal way to achieve low-cost high-performance nanoscale solar cells.
Seabuckthorn (Hippophaë rhamnoides) Freeze-Dried Powder Protects against High-Fat Diet-Induced Obesity, Lipid Metabolism Disorders by Modulating the Gut Microbiota of Mice
Authors: Guo Caixia , Han Li , Li Meiping , Yu Ligang
Published: January 2020

This study aimed to investigate the beneficial effects of seabuckthorn freeze-dried powder on high-fat diet-induced obesity and related lipid metabolism disorders, and further explored if this improvement is associated with gut microbiota. Results showed that seabuckthorn freeze-dried powder administration decreased body weight, Lee’s index, adipose tissue weight, liver weight, and serum lipid levels. Moreover, treatment with seabuckthorn freeze-dried powder effectively reduced fat accumulation by modulating the relative expression of genes involved in lipid metabolism through down-regulation of encoding lipogenic and store genes, including SREBP-1c, PPAR-γ, ACC, and SCD1, and up-regulation of regulating genes of fatty acid oxidation, including HSL, CPT-1, and ACOX. Especially, seabuckthorn freeze-dried powder regulated the composition of gut microbiota, such as increasing the ratio of Firmicutes/Bacteroidetes, decreasing relative abundance of harmful bacteria (Desulfovibrio), and increasing relative abundance of beneficial bacteria (Akkermansia and Bacteroides). The changes of beneficial bacteria had a positive correlation with genes encoding lipolysis and a negative correlation with genes encoding lipid lipogenesis and store. The harmful bacteria were just the opposite. Besides, changes in gut microbiota had an obvious effect in the secretion of main metabolites—short-chain fatty acids (SCFAs), especially propionic acid. Thus, our results indicated that the seabuckthorn freeze-dried powder could ameliorate high-fat diet-induced obesity and obesity-associated lipid metabolism disorders by changing the composition and structure of gut microbiota.
Maternal Selenium Deficiency in Mice Alters Offspring Glucose Metabolism and Thyroid Status in a Sexually Dimorphic Manner
Authors: Hofstee Pierre , McKeating Daniel R. , Bartho Lucy A. , Anderson Stephen T. , Perkins Anthony V. , Cuffe James S. M.
Published: January 2020

Selenium is an essential micronutrient commonly deficient in human populations. Selenium deficiency increases the risks of pregnancy complications; however, the long-term impact of selenium deficiency on offspring disease remains unclear. This study investigates the effects of selenium deficiency during pregnancy on offspring metabolic function. Female C57BL/6 mice were allocated to control (>190 μg selenium/kg, n = 8) or low selenium (<50 μg selenium/kg, n = 8) diets prior to mating and throughout gestation. At postnatal day (PN) 170, mice underwent an intraperitoneal glucose tolerance test and were culled at PN180 for biochemical analysis. Mice exposed to selenium deficiency in utero had reduced fasting blood glucose but increased postprandial blood glucose concentrations. Male offspring from selenium-deficient litters had increased plasma insulin levels in conjunction with reduced plasma thyroxine (tetraiodothyronine or T4) concentrations. Conversely, females exposed to selenium deficiency in utero exhibited increased plasma thyroxine levels with no change in plasma insulin. This study demonstrates the importance of adequate selenium intake around pregnancy for offspring metabolic health. Given the increasing prevalence of metabolic disease, this study highlights the need for appropriate micronutrient intake during pregnancy to ensure a healthy start to life.
Hypermutation as an Evolutionary Mechanism for Achromobacter xylosoxidans in Cystic Fibrosis Lung Infection
Authors: Veschetti Laura , Sandri Angela , Krogh Johansen Helle , Lleò Maria M. , Malerba Giovanni
Published: January 2020

Achromobacter xylosoxidans can cause chronic infections in the lungs of patients with cystic fibrosis (CF) by adapting to the specific environment. The study of longitudinal isolates allows to investigate its within-host evolution to unravel the adaptive mechanisms contributing to successful colonization. In this study, four clinical isolates longitudinally collected from two chronically infected patients underwent whole genome sequencing, de novo assembly and sequence analysis. Phenotypic assays were also performed. The isolates coming from one of the patients (patient A) presented a greater number of genetic variants, diverse integrative and conjugative elements, and different protease secretion. In the first of these isolates (strain A1), we also found a large deletion in the mutS gene, involved in DNA mismatch repair (MMR). In contrast, isolates from patient B showed a lower number of variants, only one integrative and mobilizable element, no phenotypic changes, and no mutations in the MMR system. These results suggest that in the two patients the establishment of a chronic infection was mediated by different adaptive mechanisms. While the strains isolated from patient B showed a longitudinal microevolution, strain A1 can be clearly classified as a hypermutator, confirming the occurrence and importance of this adaptive mechanism in A. xylosoxidans infection.
Enniatin Production Influences Fusarium avenaceum Virulence on Potato Tubers, but not on Durum Wheat or Peas
Authors: Eranthodi Anas , Schneiderman Danielle , Harris Linda J. , Witte Thomas E. , Sproule Amanda , Hermans Anne , Overy David P. , Chatterton Syama , Liu Jiajun , Li Tao , González-Peña Fundora Dianevys , Zhao Weiquan , Foroud Nora A.
Published: January 2020

Fusarium avenaceum is a generalist pathogen responsible for diseases in numerous crop species. The fungus produces a series of mycotoxins including the cyclohexadepsipeptide enniatins. Mycotoxins can be pathogenicity and virulence factors in various plant–pathogen interactions, and enniatins have been shown to influence aggressiveness on potato tubers. To determine the role of these mycotoxins in other F. avenaceum–host interactions, ENNIATIN SYNTHASE 1 (ESYN1) disruption and overexpression mutants were generated and their ability to infect wheat and peas investigated. As a preliminary study, the transformants were screened for their ability to cause potato tuber necrosis and, consistent with a previous report, enniatin production increased necrotic lesion size on the tubers. By contrast, when the same mutants were assessed in their ability to cause disease in pea roots or durum wheat spikes, no changes in disease symptoms or virulence were observed. While it is known that, at least in the case of wheat, exogenously applied enniatins can cause tissue necrosis, this group of mycotoxins does not appear to be a key factor on its own in disease development on peas or durum wheat.
Peptide-Based Soft Hydrogels Modified with Gadolinium Complexes as MRI Contrast Agents
Authors: Gallo Enrico , Diaferia Carlo , Di Gregorio Enza , Morelli Giancarlo , Gianolio Eliana , Accardo Antonella
Published: January 2020

Poly-aromatic peptide sequences are able to self-assemble into a variety of supramolecular aggregates such as fibers, hydrogels, and tree-like multi-branched nanostructures. Due to their biocompatible nature, these peptide nanostructures have been proposed for several applications in biology and nanomedicine (tissue engineering, drug delivery, bioimaging, and fabrication of biosensors). Here we report the synthesis, the structural characterization and the relaxometric behavior of two novel supramolecular diagnostic agents for magnetic resonance imaging (MRI) technique. These diagnostic agents are obtained for self-assembly of DTPA(Gd)-PEG8-(FY)3 or DOTA(Gd)-PEG8-(FY)3 peptide conjugates, in which the Gd-complexes are linked at the N-terminus of the PEG8-(FY)3 polymer peptide. This latter was previously found able to form self-supporting and stable soft hydrogels at a concentration of 1.0% wt. Analogously, also DTPA(Gd)-PEG8-(FY)3 and DOTA(Gd)-PEG8-(FY)3 exhibit the trend to gelificate at the same range of concentration. Moreover, the structural characterization points out that peptide (FY)3 moiety keeps its capability to arrange into β-sheet structures with an antiparallel orientation of the β-strands. The high relaxivity value of these nanostructures (~12 mM−1·s−1 at 20 MHz) and the very low in vitro cytotoxicity suggest their potential application as supramolecular diagnostic agents for MRI.
Ultrahigh-Resolution Optical Vector Analyzers
Authors: Morozov Oleg , Nureev Ilnur , Sakhabutdinov Airat , Kuznetsov Artem , Morozov Gennady , Il’in German , Papazyan Samvel , Ivanov Alexander , Ponomarev Roman
Published: January 2020

The optical vector analyzer is a device used to measure the magnitude, phase responses, and other parameters of optical devices. There have been increasingly higher demands placed on optical vector analyzers during the development of optical technologies, which are satisfied by the creation of new devices and their operating principles. For further development in this area, it is necessary to generalize the experience gained during the development of optical vector analyzers. Thus, in this report, we provide an overview of all the basic types of approaches used for the realization of optical vector analyzers, including the advanced ones with the best performances. The principles of their working, as well as their associated advantages, disadvantages, and existing solutions to the identified problems, are examined in detail. The presented approaches could be of value and interest to those working in the field of laser dynamics and optical devices, as we propose one use of the optical vector analyzer as being the characterization of Fano resonance structures.
Ultra-Wideband WDM Optical Network Optimization
Authors: Kozdrowski Stanisław , Żotkiewicz Mateusz , Sujecki Sławomir
Published: January 2020

Ultra-wideband wavelength division multiplexed networks enable operators to use more effectively the bandwidth offered by a single fiber pair and thus make significant savings, both in operational and capital expenditures. The main objective of this study is to minimize optical node resources, such as transponders, multiplexers and wavelength selective switches, needed to provide and maintain high quality of network services, in ultra-wideband wavelength division multiplexed networks, at low cost. A model based on integer programming is proposed, which includes a detailed description of optical network nodal resources. The developed optimization tools are used to study the ultra-wideband wavelength division multiplexed network performance when compared with the traditional C-band wavelength division multiplexed networks. The analysis is carried out for realistic networks of different dimensions and traffic demand sets.
Leaves of Invasive Plants—Japanese, Bohemian and Giant Knotweed—The Promising New Source of Flavan-3-ols and Proanthocyanidins
Authors: Bensa Maja , Glavnik Vesna , Vovk Irena
Published: January 2020

This is the first report on identification of all B-type proanthocyanidins from monomers to decamers (monomers—flavan-3-ols, dimers, trimers, tetramers, pentamers, hexamers, heptamers, octamers, nonamers, and decamers) and some of their gallates in leaves of Japanese knotweed (Fallopia japonica Houtt.), giant knotweed (Fallopia sachalinensis F. Schmidt) and Bohemian knotweed (Fallopia × bohemica (Chrtek & Chrtkova) J.P. Bailey). Flavan-3-ols and proanthocyanidins were investigated using high performance thin-layer chromatography (HPTLC) coupled to densitometry, image analysis, and mass spectrometry (HPTLC–MS/MS). All species contained (−)-epicatechin and procyanidin B2, while (+)-catechin was only detected in Bohemian and giant knotweed. (−)-Epicatechin gallate, procyanidin B1 and procyanidin C1 was only confirmed in giant knotweed. Leaves of all three knotweeds have the same chemical profiles of proanthocyanidins with respect to the degree of polymerization but differ with respect to gallates. Therefore, chromatographic fingerprint profiles of proanthocyanidins enabled differentiation among leaves of studied knotweeds, and between Japanese knotweed leaves and rhizomes. Leaves of all three species proved to be a rich source of proanthocyanidins (based on the total peak areas), with the highest content in giant and the lowest in Japanese knotweed. The contents of monomers in Japanese, Bohemian and giant knotweed were 0.84 kg/t of dry weight (DW), 1.39 kg/t DW, 2.36 kg/t, respectively, while the contents of dimers were 0.99 kg/t DW, 1.40 kg/t, 2.06 kg/t, respectively. Giant knotweed leaves showed the highest variety of gallates (dimer gallates, dimer digallates, trimer gallates, tetramer gallates, pentamer gallates, and hexamer gallates), while only monomer gallates and dimer gallates were confirmed in Japanese knotweed and monomer gallates, dimer gallates, and dimer digallates were detected in leaves of Bohemian knotweed. The profile of the Bohemian knotweed clearly showed the traits inherited from Japanese and giant knotweed from which it originated.
Acknowledgement to Reviewers of Plants in 2019
Authors:   Plants Editorial Office
Published: January 2020

The editorial team greatly appreciates the reviewers who have dedicated their considerable time and expertise to the journal’s rigorous editorial process over the past 12 months, regardless of whether the papers are finally published or not [...]
Settling for Less: Do Statoliths Modulate Gravity Perception?
Authors: Ditengou Franck Anicet , Teale William David , Palme Klaus
Published: January 2020

Plants orientate their growth either towards (in roots) or away from (in shoots) the Earth’s gravitational field. While we are now starting to understand the molecular architecture of these gravity response pathways, the gravity receptor remains elusive. This perspective looks at the biology of statoliths and suggests it is conceivable that their immediate environment may be tuned to modulate the strength of the gravity response. It then suggests how mutant screens could use this hypothesis to identify the gravity receptor.