bluuebunny/crossref_metadata_2025 huggingface dataset:
Effects of Metformin on Risk and Prognosis of Biliary Tract Cancer: A Systematic Review and Meta-Analysis
Authors: Chen Junhong , Jin Hengwei , Zhou Hao , Liu Kai
Published: February 2023

Background and Objectives: Metformin has been found to potentially reduce the risk and improve the prognosis of a variety of tumors, but these findings remain controversial in biliary tract cancer (BTC). Therefore, this systematic review and meta-analysis was conducted to investigate the association between metformin and BTC. Materials and Methods: Two independent researchers comprehensively searched PubMed, Embase, the Cochrane Library, and Web of Science for eligible studies published from their inception to 31 March 2022. Comparisons of risk, overall survival (OS), and disease-free survival (DFS) for patients with BTC were selected as the endpoints of interest and pooled by random or fixed-effects models. Results: Eleven studies with a total of 24,788,738 participants were eligible for this analysis. The overall pooled effects showed no significant differences in biliary tract cancer risk (hazard ratio (HR) = 0.82, 95% confidence interval (CI): 0.50–1.35, p = 0.436), OS (HR = 0.88, 95% CI: 0.74–1.04, p = 0.135), or DFS (HR = 1.03, 95% CI: 0.79–1.34, p = 0.829) between metformin users and non-users. When restricting participants to those with diabetes, a similar negative result was found, demonstrating that metformin use was not significantly associated with a lower risk of developing BTC compared with a lack of metformin use (HR = 0.65, 95% CI: 0.39–1.07, p = 0.089); notably, the included studies exhibited significant heterogeneity in the selection of participants and the definition of metformin users. Conclusions: Metformin may not be able to reduce the risk of BTC and improve prognosis in certain populations. Based on the limited quantity and quality of the included studies, the present results should be interpreted within their limitations, and further studies are warranted to determine the optimal timing, dose, duration, and scenario of metformin administration.
Mannosylated-Chitosan-Coated Andrographolide Nanoliposomes for the Treatment of Hepatitis: In Vitro and In Vivo Evaluations
Authors: Metkar Sayali Pravin , Fernandes Gasper , Nikam Ajinkya Nitin , Soman Soji , Birangal Sumit , Seetharam Raviraja N , Joshi Manjunath Bandu , Mutalik Srinivas
Published: February 2023

A key diterpene lactone of Andrographis paniculata, i.e., andrographolide (AG), exhibits a variety of physiological properties, including hepatoprotection. The limited solubility, short half-life, and poor bioavailability limits the pharmacotherapeutic potential of AG. Therefore, in this study we aimed to formulate and optimize AG-loaded nanoliposomes (AGL) using the Design of Experiment (DOE) approach and further modify the surface of the liposomes with mannosylated chitosan to enhance its oral bioavailability. Physical, morphological, and solid-state characterization was performed to confirm the formation of AGL and Mannosylated chitosan-coated AGL (MCS-AGL). Molecular docking studies were conducted to understand the ligand (MCS) protein (1EGG) type of interaction. Further, in vitro release, ex vivo drug permeation, and in vivo pharmacokinetics studies were conducted. The morphological studies confirmed that AGL was spherical and a layer of MCS coating was observed on their surface, forming the MCS-AGL. Further increase in the particle size and change in the zeta potential of MCS-AGL confirms the coating on the surface of AGL (375.3 nm, 29.80 mV). The in vitro drug release data reflected a sustained drug release profile from MCS-AGL in the phosphate buffer (pH 7.4) with 89.9 ± 2.13% drug release in 8 h. Ex vivo permeation studies showed higher permeation of AG from MCS-AGL (1.78-fold) compared to plain AG and AGL (1.37-fold), indicating improved permeability profiles of MCS-AGL. In vivo pharmacokinetic studies inferred that MCS-AGL had a 1.56-fold enhancement in AUC values compared to plain AG, confirming that MCS-AGL improved the bioavailability of AG. Additionally, the 2.25-fold enhancement in the MRT proves that MCS coating also enhances the in vivo stability and retention of AG (stealth effect). MCS as a polymer therefore has a considerable potential for improving the intestinal permeability and bioavailability of poorly soluble and permeable drugs or phytoconstituents when coated over nanocarriers.
Metabolic Signatures Elucidate the Effect of Body Mass Index on Type 2 Diabetes
Authors: Dong Qiuling , Sidra Sidra , Gieger Christian , Wang-Sattler Rui , Rathmann Wolfgang , Prehn Cornelia , Adamski Jerzy , Koenig Wolfgang , Peters Annette , Grallert Harald , Sharma Sapna
Published: February 2023

Obesity plays an important role in the development of insulin resistance and diabetes, but the molecular mechanism that links obesity and diabetes is still not completely understood. Here, we used 146 targeted metabolomic profiles from the German KORA FF4 cohort consisting of 1715 participants and associated them with obesity and type 2 diabetes. In the basic model, 83 and 51 metabolites were significantly associated with body mass index (BMI) and T2D, respectively. Those metabolites are branched-chain amino acids, acylcarnitines, lysophospholipids, or phosphatidylcholines. In the full model, 42 and 3 metabolites were significantly associated with BMI and T2D, respectively, and replicate findings in the previous studies. Sobel mediation testing suggests that the effect of BMI on T2D might be mediated via lipids such as sphingomyelin (SM) C16:1, SM C18:1 and diacylphosphatidylcholine (PC aa) C38:3. Moreover, mendelian randomization suggests a causal relationship that BMI causes the change of SM C16:1 and PC aa C38:3, and the change of SM C16:1, SM C18:1, and PC aa C38:3 contribute to T2D incident. Biological pathway analysis in combination with genetics and mice experiments indicate that downregulation of sphingolipid or upregulation of phosphatidylcholine metabolism is a causal factor in early-stage T2D pathophysiology. Our findings indicate that metabolites like SM C16:1, SM C18:1, and PC aa C38:3 mediate the effect of BMI on T2D and elucidate their role in obesity related T2D pathologies.
Metabolites That Confirm Induction and Release of Dormancy Phases in Sweet Cherry Buds
Authors: Götz Klaus-P. , Chmielewski Frank-M.
Published: February 2023

Here we report on metabolites found in a targeted profiling of ‘Summit’ flower buds for nine years, which could be indicators for the timing of endodormancy release (t1) and beginning of ontogenetic development (t1*). Investigated metabolites included chrysin, arabonic acid, pentose acid, sucrose, abscisic acid (ABA), and abscisic acid glucose ester (ABA-GE). Chrysin and water content showed an almost parallel course between leaf fall and t1*. After ‘swollen bud’, water content raised from ~60 to ~80% at open cluster, while chrysin content decreased and lost its function as an acetylcholinesterase inhibitor. Both parameters can be suitable indicators for t1*. Arabonic acid showed a clear increase after t1*. Pentose acid would be a suitable metabolite to identify t1 and t1*, but would not allow describing the ecodormancy phase, because of its continuously low value during this time. Sucrose reached a maximum during ecodormancy and showed a significant correlation with air temperature, which confirms its cryoprotective role in this phase. The ABA content showed maximum values during endodormancy and decreased during ecodormancy, reaching 50% of its content t1 at t1*. It appears to be the key metabolite to define the ecodormancy phase. The ABA-GE was present at all stages and phases and was much higher than the ABA content and is a readily available storage pool in cherry buds.
Lower Glucose Effectiveness Is Associated with Subclinical Reactive Hypoglycemia, Snacking Habits, and Obesity
Authors: Kishimoto Ichiro , Ohashi Akio
Published: February 2023

The effects of glucose effectiveness, the insulin-independent mechanism of glucose disposal, on hypoglycemia have not yet been fully investigated. Herein, in 50 males without a diagnosis of diabetes mellitus (median age 54 years, body mass index (BMI) ≥ 25), the index of glucose effectiveness (SgIo) was determined by a 75 g oral glucose tolerance test (OGTT), and continuous glucose monitoring (CGM) was performed for 6 days. The minimal glucose levels and the percentages of time below 70 mg/dL (3.9 mmol/L) (TBR70) during CGM were significantly associated with the SgIo tertile category in a biphasic manner. When TBR70 within 24 h after OGTT ≥ 0.6% was defined as subclinical reactive hypoglycemia (SRH), odds ratios of having SRH in SgIo tertile 1 (lowest) and tertile 3 (highest) compared to SgIo tertile 2 (middle) were both 11.7 (p = 0.007), while the odds ratios of the highest post-load insulin quartile were 22.9 (p = 0.001) and 1.07 (p = 0.742), respectively. The chances of having self-reported snacking habits, obesity (BMI ≥ 30), and impaired glucose tolerance were significantly higher in participants in SgIo tertile 1 compared to those in SgIo tertile 2, with odds ratios of 10.7 (p = 0.005), 11.2 (p = 0.02), and 13.8 (p = 0.002), respectively. However, there was no significant difference between SgIo tertile categories 2 and 3. In conclusion, SgIo is associated with SRH in a biphasic manner. In people with lower glucose effectiveness, the SRH-induced increase in appetite may create a vicious cycle that leads to obesity.
Pyrite Sulfur Isotope Systematics Suggest Low Marine Sulfate Levels across the Ediacaran–Cambrian Transition
Authors: Li Songzhuo , Lang Xianguo , Wang Han , Zhu Shengxian , Zhao Kun , Hou Mingcai
Published: February 2023

The Ediacaran–Cambrian (E–C) transition was a critical period in Earth’s history, and it was characterized by variable but potentially significant increases in atmospheric oxygen levels (pO2). Sulfate is an essential oxidant and plays a key role in regulating Earth’s surface redox conditions. However, there is uncertainty regarding seawater sulfate levels during the E–C transition. To address this issue, organic carbon (δ13Corg) and pyrite sulfur isotope (δ34Spy) analyses of the Heyu section (the Dengying Formation) in the Sichuan Basin, South China, were carried out. The δ13Corg varies between −36.4‰ and −27.4‰, and δ34Spy ranges from −6.6‰ to 27.3‰. The TOC and pyrite content ranges from 0.13 wt.% to 4.28 wt.% and from 0.01 wt.% to 0.94 wt.%, respectively. The marine sulfate concentration was modeled using a one-dimensional diffusion–advection–reaction model (1D-DAR). The modeling results indicate that the seawater sulfate level remained at a relatively low level of ~2–6 mM. The increased pyrite burial at extensive marine anoxia during the terminal Ediacaran period was likely a driver of such a low sulfate level.
Molecular Dynamics Simulation of Methane Adsorption and Diffusion: A Case Study of Low-Rank Coal in Fukang Area, Southern Junggar Basin
Authors: Xiang Jie , Li Xianqing , Gao Weiyu , Liu Yu , Li Jiandong , Yang Jingwei , Gong Yixiao
Published: February 2023

Adsorption and diffusion are the key factors affecting coalbed methane (CBM) accumulation, resource assessment and production prediction. To study the adsorption and diffusion mechanism of Fukang low-rank coal at the microscopic level, samples of Fukang low-rank coal were collected, and the elemental composition, carbon type distribution and functional group type of the Fukang low-rank coal structure were determined by elemental analysis (Ea), Fourier-transform interferometric radiometer (FTIR), X-ray photoelectron spectroscopy (XPS) and 13C nuclear magnetic resonance (13C NMR) experiments to construct a 2D molecular structure of the coal and a 3D macromolecular structure model. The adsorption and diffusion characteristics of methane were researched by giant regular Monte Carlo (GCMC) and molecular dynamics (MD) simulation methods. The results showed that the excess adsorption amount of methane increased and then decreased with the increase in pressure. The diffusion of methane showed two stages with increasing pressure: a sharp decrease in the diffusion coefficient from 0.5 to 5.0 MPa and a slow decrease in the diffusion coefficient from 5.0 to 15.0 MPa. The lower the pressure, the larger the effective radius of the CH4 and C atoms, and the higher the temperature, the more pronounced the diffusion and the larger the effective radius.
Tungsten-Bearing Wodginite from the Kester Deposit, Eastern Siberia, Russia
Authors: Alekseev Viktor I. , Alekseev Ivan V.
Published: February 2023

Li-F granites from the Kester deposit (Yana Plateau in Yakutia, Russia) are proved to be connected with a rare-metal complex of accessory minerals: montebrasite, columbite-(Mn), columbite-(Fe), tantalite-(Mn), Ta-bearing cassiterite, U-bearing microlite, W-bearing ixiolite, niobian ferberite, U–Hf-rich zircon, and Ta-bearing rutile. Accessory wodginite was discovered at depths of up to 150 m in association with tantalite-(Mn), columbite-(Mn), and cassiterite. According to the content of WO3 (1.23%–3.33%) and the values of Mn/(Mn + Fet) and Ta/(Ta + Nb), Yakut wodginite is an intermediate mineral between wodginite and a hypothetical mineral of the wodginite group—”wolframowodginite”. The discovery of tungsten-bearing wodginite at the Kester deposit confirms the widespread presence of tungstic and tungsten-bearing accessory minerals in Li-F granites in the Russian Far East. It also serves as an indicator of rare-metal tin-tantalum-bearing granites and pegmatites.
Novel Indane Derivatives with Antioxidant Activity from the Roots of Anisodus tanguticus
Authors: Meng Chun-Wang , Zhao Hao-Yu , Zhu Huan , Peng Cheng , Zhou Qin-Mei , Xiong Liang
Published: February 2023

Four novel indane derivatives, anisotindans A–D (1–4), were isolated from the roots of Anisodus tanguticus. Their structures were established using comprehensive spectroscopic analyses, and their absolute configurations were determined by electronic circular dichroism (ECD) calculations and single-crystal X-ray diffraction analyses. Anisotindans C and D (3 and 4) are two unusual indenofuran analogs. ABTS•+ and DPPH•+ assays of radical scavenging activity reveal that all compounds (1–4) are active. Specifically, the ABTS•+ assay results show that anisotindan A (1) exhibits the best antioxidant activity with an IC50 value of 15.62 ± 1.85 μM (vitamin C, IC50 = 22.54 ± 5.18 μM).
A Review of Different Types of Liposomes and Their Advancements as a Form of Gene Therapy Treatment for Breast Cancer
Authors: Tseu Gloria Yi Wei , Kamaruzaman Khairul Azfar
Published: February 2023

Breast cancer incidence and mortality rates have increased exponentially during the last decade, particularly among female patients. Current therapies, including surgery and chemotherapy, have significant negative physical and mental impacts on patients. As a safer alternative, gene therapy utilising a therapeutic gene with the potential to treat various ailments is being considered. Delivery of the gene generally utilises viral vectors. However, immunological reactions and even mortality have been recorded as side effects. As a result, non-viral vectors, such as liposomes, a system composed of lipid bilayers formed into nanoparticles, are being studied. Liposomes have demonstrated tremendous potential due to their limitless ability to combine many functions into a system with desirable characteristics and functionality. This article discusses cationic, anionic, and neutral liposomes with their stability, cytotoxicity, transfection ability, cellular uptake, and limitation as a gene carrier suitable for gene therapy specifically for cancer. Due to the more practical approach of employing electrostatic contact with the negatively charged nucleic acid and the cell membrane for absorption purposes, cationic liposomes appear to be more suited for formulation for gene delivery and therapy for breast cancer treatment. As the other alternatives have numerous complicated additional modifications, attachments need to be made to achieve a functional gene therapy system for breast cancer treatment, which were also discussed in this review. This review aimed to increase understanding and build a viable breast cancer gene therapy treatment strategy.
Searching for the Best Values of NMR Shielding and Spin-Spin Coupling Parameters: CH4-nFn Series of Molecules as the Example
Authors: Jackowski Karol , Słowiński Mateusz A.
Published: February 2023

Attempts at the theoretical interpretation of NMR spectra have a very long and fascinating history. Present quantum chemical calculations of shielding and indirect spin-spin couplings permit modeling NMR spectra when small, isolated molecules are studied. Similar data are also available from NMR experiments if investigations are performed in the gas phase. An interesting set of molecules is formed when a methane molecule is sequentially substituted by fluorine atoms—CH4-nFn, where n = 0, 1, 2, 3, or 4. The small molecules contain up to three magnetic nuclei, each with a one-half spin number. The spectral parameters of CH4-nFn can be easily observed in the gas phase and calculated with high accuracy using the most advanced ab initio methods of quantum chemistry. However, the presence of fluorine atoms makes the calculations of shielding and spin-spin coupling constants extremely demanding. Appropriate experimental 19F NMR parameters are good but also require some further improvements. Therefore, there is a real need for the comparison of existing NMR measurements with available state-of-the-art theoretical results for a better understanding of actual limits in the determination of the best shielding and spin-spin coupling values, and CH4-nFn molecules are used here as the exceptionally important case.
Developing a Compost Quality Index (CQI) Based on the Electrochemical Quantification of Cd (HA) Reactivity
Authors: Silva Ana C. , Rocha Pedro , Geraldo Dulce , Cunha Ana , Antelo Juan , Pinheiro José P. , Fiol Sarah , Bento Fátima
Published: February 2023

The present work demonstrates the use of Cd2+ as a reactivity probe of the fulvic acids (FAs), humic acids (HAs) and dissolved organic matter (DOM) compost extracts. Significant differences were observed between the extracts, with the HA extract showing the highest reactivity. Comparing the different composts, the largest reactivity variation was again observed for HA then FA and finally DOM extracts. The Cd2+ binding extent was used to calculate the quality of composts and compared with a reference of uncomposted organic fertiliser (FLW), leading to the definition of an operational scale of compost quality. The parameter equivalent mass of fertiliser (mEF) was used for this scale sorted the seven composts from 0.353 to 1.09 kg FLW, for compost of sewage sludge (CSS) and vermicompost of domestic waste (CVDW), respectively. The significance of this parameter was verified through a correlation analysis between binding extent and the effect of compost application on lettuce crop growth in a field trial. The results demonstrate the potentiality of FA and HA extracts as markers of compost bioactivity and the use of Cd2+ as a reactivity probe.
Investigation on Gold–Ligand Interaction for Complexes from Gold Leaching: A DFT Study
Authors: Zhang Na , Kou Jue , Sun Chunbao
Published: February 2023

Gold leaching is an important process to extract gold from ore. Conventional alkaline cyanide process and alternative nontoxic lixiviants including thiosulfate, thiourea, thiocyanate, and halogen have been widely investigated. However, density functional theory (DFT) study on the gold complexes Au(CN)2−, Au(S2O3)23−, Au[SC(NH2)2]2+, Au(SCN)2−, and AuCl2− required for discovering and designing new highly efficient and environmentally friendly gold leaching reagents is lacking, which is expected to support constructive information for the discovery and designation of new high-efficiency and environmentally friendly gold leaching reagents. In this study, the structure information, electron-transferring properties, orbital interaction, and chemical bond composition for complexes Au(CN)2−, Au(S2O3)23−, Au[SC(NH2)2]2+, Au(SCN)2−, and AuCl2− depending on charge decomposition analysis (CDA), natural bond orbital (NBO), natural resonance theory (NRT), electron localization function (ELF), and energy decomposition analysis (EDA) were performed based on DFT calculation. The results indicate that there is not only σ-donation from ligand to Au+, but also electron backdonation from Au+ to ligands, which strengthens the coordinate bond between them. Compared with Cl−, ligands CN−, S2O32−, SC(NH2)2, and SCN− have very large covalent contribution to the coordinate bond with Au+, which explains the special stability of Au-CN and Au-S bonds. The degree of covalency and bond energy in Au–ligand bonding decreases from Au(CN)2−, Au(S2O3)23−, Au[SC(NH2)2]2+, Au(SCN)2−, to AuCl2−, which interprets the stability of the five complexes: Au(CN)2− > Au(S2O3)23− > Au[SC(NH2)2]2+ > Au(SCN)2− > AuCl2−.
Cytotoxic and Antioxidant Activity of Hypericum perforatum L. Extracts against Human Melanoma Cells from Different Stages of Cancer Progression, Cultured under Normoxia and Hypoxia
Authors: Brankiewicz Aleksandra , Trzos Sara , Mrożek Magdalena , Opydo Małgorzata , Szostak Elżbieta , Dziurka Michał , Tuleja Monika , Łoboda Agnieszka , Pocheć Ewa
Published: February 2023

Oxidative stress and the hypoxic microenvironment play a key role in the progression of human melanoma, one of the most aggressive skin cancers. The aim of our study was to evaluate the effect of Hypericum perforatum extracts of different origins (both commercially available (HpEx2) and laboratory-prepared from wild grown (HpEx12) and in vitro cultured (HpEx13) plants) and hyperforin salt on WM115 primary and WM266-4 lymph node metastatic human melanoma cells cultured under normoxic and hypoxic conditions. The polyphenol content, radical scavenging activity, and hyperforin concentration were determined in the extracts, while cell viability, apoptosis, ROS production, and expression of NRF2 and HO-1, important oxidative stress-related factors, were analyzed after 24 h of cell stimulation with HpExs and hyperforin salt. We found that cytotoxic, pro-apoptotic and antioxidant effects depend on the extract composition, the stage of melanoma progression, and the oxygen level. Hyperforin salt showed lower activity than H. perforatum extracts. Our study for the first time showed that the anticancer activity of H. perforatum extracts differs in normoxia and hypoxia. Importantly, the composition of extracts of various origins, including in vitro cultured, resulting in their unique properties, may be important in the selection of plants for therapeutic application.
Biodiesel Purification by Solvent-Aided Crystallization Using 2-Methyltetrahydrofuran
Authors: Wan Osman Wan Nur Aisyah , Badrol Nur Athirah Izzati , Samsuri Shafirah
Published: February 2023

The previous biodiesel purification by Solvent-Aided Crystallization (SAC) using 1-butanol as assisting agent and parameters for SAC were optimized such as coolant temperature, cooling time and stirring speed. Meanwhile, 2-Methyltetrahydrofuran (2-MeTHF) was selected as an alternative to previous organic solvents for this study. In this context, it is used to replace solvent 1-butanol from a conducted previous study. This study also focuses on the technological improvements in the purification of biodiesel via SAC as well as to produce an even higher purity of biodiesel. Experimental works on the transesterification process to produce crude biodiesel were performed and SAC was carried out to purify the crude biodiesel. The crude biodiesel content was analyzed by using Gas Chromatography–Mass Spectrometry (GC-MS) and Differential Scanning Calorimetry (DSC) to measure the composition of Fatty Acid Methyl Esters (FAME) present. The optimum value to yield the highest purity of FAME for parameters coolant temperature, cooling time, and stirring speed is −4 °C, 10 min and 210 rpm, respectively. It can be concluded that the assisting solvent 2-MeTHF has a significant effect on the process parameters to produce purified biodiesel according to the standard requirement.
Semi-Polycrystalline Polyaniline-Activated Carbon Composite for Supercapacitor Application
Authors: Mahato Neelima , Sreekanth T. V. M. , Yoo Kisoo , Kim Jonghoon
Published: February 2023

We report on the synthesis of activated carbon-semi-polycrystalline polyaniline (SPani-AC) composite material using in-situ oxidative polymerization of aniline on the carbon surface in an aqueous HCl medium at an elevated temperature of 60 °C. The electroactive polymeric composite material exhibits a uniformly distributed spindle-shaped morphology in scanning electron microscopy (SEM) and well-defined crystallographic lattices in the high-resolution transmission electron microscopy (TEM) images. The X-ray diffraction (XRD) spectrum reveals sharp peaks characteristic of crystalline polyaniline. The characteristic chemical properties of polyaniline are recorded using laser Raman spectroscopy. The cyclic voltammetry curves exhibit features of surface-redox pseudocapacitance. The specific capacitance calculated for the material is 507 F g−1 at the scan rate of 10 mV s−1. The symmetrical two-electrodes device exhibits a specific capacitance of 45 F g−1 at a current density of 5 A g−1. The capacitive retention calculated was found to be 96% up to 4500 continuous charge–discharge cycles and observed to be gradually declining at the end of 10,000 cycles. On the other hand, Coulombic efficiency was observed to be retained up to 85% until 4500 continuous charge–discharge cycles which declines up to 72% at the end of 10,000 cycles. The article also presents a detailed description of material synthesis, the formation of polyaniline (Pani) chains, and the role of material architecture in the performance as surface redox supercapacitor electrode.
New Verticillene Diterpenoids, Eudesmane Sesquiterpenoids, and Hydroperoxysteroids from the Further Chemical Investigation of a Taiwanese Soft Coral Cespitularia sp.
Authors: Fu Chung-Wei , Lin You-Cheng , Chiou Shu-Fen , Chen Shu-Li , Lin Chi-Chien , Wang Hui-Chun , Dai Chang-Feng , Sheu Jyh-Horng
Published: February 2023

An investigation of the chemical composition of a Formosan soft coral Cespitularia sp. led to the discovery of one new verticillene-type diterpenoid, cespitulactam M (1); one new eudesmane sesquiterpenoid, cespilamide F (2); and three new hydroperoxysteroids (3–5) along with twelve known analogous metabolites (6–17). In addition, one new derivative, cespitulactam M-6,2′-diacetate (1a), was prepared from compound 1. The structures were determined by detailed spectroscopic analyses, particularly HRESIMS and NMR techniques. Moreover, the in vitro cytotoxicity, anti-inflammatory, and antibacterial activity of 1–17 and 1a were evaluated.
Interfaces and Oxygen Vacancies-Enriched Catalysts Derived from Cu-Mn-Al Hydrotalcite towards High-Efficient Water–Gas Shift Reaction
Authors: Li Hanci , Xiao Zhenyi , Liu Pei , Wang Hairu , Geng Jiajun , Lei Huibin , Zhuo Ou
Published: February 2023

The water–gas shift (WGS) reaction is an important process in the hydrogen industry, and its catalysts are of vital importance for this process. However, it is still a great challenge to develop catalysts with both high activity and high stability. Herein, a series of high-purity Cu-Mn-Al hydrotalcites with high Cu content have been prepared, and the WGS performance of the Cu-Mn-Al catalysts derived from these hydrotalcites have been studied. The results show that the Cu-Mn-Al catalysts have both outstanding catalytic activity and excellent stability. The optimized Cu-Mn-Al catalyst has displayed a superior reaction rate of 42.6 μmolCO−1⋅gcat−1⋅s−1, while the CO conversion was as high as 96.1% simultaneously. The outstanding catalytic activities of the Cu-Mn-Al catalysts could be ascribed to the enriched interfaces between Cu-containing particles and manganese oxide particles, and/or abundant oxygen vacancies. The excellent catalytic stability of the Cu-Mn-Al catalysts may be benefitting from the low valence state of the manganese of manganese oxides, because the low valence manganese oxides have good anti-sintering properties and can stabilize oxygen vacancies. This study provides an example for the construction of high-performance catalysts by using two-dimensional hydrotalcite materials as precursors.
Unprecedented Elimination Reactions of Cyclic Aldols: A New Biosynthetic Pathway toward the Taiwaniaquinoid Skeleton
Authors: Guardia Juan J. , Fernández Antonio , Justicia José , Zentar Houda , Alvarez-Manzaneda Ramón , Alvarez-Manzaneda Enrique , Chahboun Rachid
Published: February 2023

The acid treatment of 6,7-seco-abietane dialdehydes gives, in high yield, the corresponding derivatives with the 4a-methyltetrahydrofluorene skeleton of taiwaniaquinoids. A mechanism involving the elimination of formic acid from the cyclic aldol intermediate is proposed here. This process can be postulated as a new biogenetic pathway from abietane diterpenes to taiwaniaquinoids. Using this novel reaction, the first enantiospecific synthesis of bioactive natural cupresol and taxodal has been obtained.
Phenolic Acids and Amaryllidaceae Alkaloids Profiles in Leucojum aestivum L. In Vitro Plants Grown under Different Light Conditions
Authors: Morańska Emilia , Simlat Magdalena , Warchoł Marzena , Skrzypek Edyta , Waligórski Piotr , Laurain-Mattar Dominique , Spina Rosella , Ptak Agata
Published: February 2023

Light-emitting diodes (LEDs) have emerged as efficient light sources for promoting in vitro plant growth and primary and secondary metabolite biosynthesis. This study investigated the effects of blue, red, and white-red LED lights on plant biomass growth, photosynthetic pigments, soluble sugars, phenolic compounds, the production of Amaryllidaceae alkaloids, and the activities of antioxidant enzymes in Leucojum aestivum L. cultures. A white fluorescent light was used as a control. The plants that were grown under white-red and red light showed the highest fresh biomass increments. The blue light stimulated chlorophyll a, carotenoid, and flavonoid production. The white-red and blue lights were favourable for phenolic acid biosynthesis. Chlorogenic, p-hydroxybenzoic, caffeic, syringic, p-coumaric, ferulic, sinapic, and benzoic acids were identified in plant materials, with ferulic acid dominating. The blue light had a significant beneficial effect both on galanthamine (4.67 µg/g of dry weight (DW)) and lycorine (115 µg/g DW) biosynthesis. Red light treatment increased catalase and superoxide dismutase activities, and high catalase activity was also observed in plants treated with white-red and blue light. This is the first report to provide evidence of the effects of LED light on the biosynthesis of phenolic acid and Amaryllidaceae alkaloids in L. aestivum cultures, which is of pharmacological importance and can propose new strategies for their production.
Niobium: The Focus on Catalytic Application in the Conversion of Biomass and Biomass Derivatives
Authors: Oliveira Luiz , Pereira Márcio , Pacheli Heitman Ana , Filho José , Oliveira Cinthia , Ziolek Maria
Published: February 2023

The world scenario regarding consumption and demand for products based on fossil fuels has demonstrated the imperative need to develop new technologies capable of using renewable resources. In this context, the use of biomass to obtain chemical intermediates and fuels has emerged as an important area of research in recent years, since it is a renewable source of carbon in great abundance. It has the benefit of not contributing to the additional emission of greenhouse gases since the CO2 released during the energy conversion process is consumed by it through photosynthesis. In the presented review, the authors provide an update of the literature in the field of biomass transformation with the use of niobium-containing catalysts, emphasizing the versatility of niobium compounds for the conversion of different types of biomass.
Ruthenium(II) Complexes Coupled by Erianin Via a Flexible Carbon Chain as a Potential Stabilizer of c-myc G-Quadruplex DNA
Authors: Wang Zhixiang , Liu Wentao , Li Guohu , Wang Jiacheng , Zhao Bin , Huang Peishan , Mei Wenjie
Published: February 2023

Herein, two novel ruthenium(II) complexes coupled by erianin via a flexible carbon chain, [Ru(phen)2(L1-(CH2)4-erianin)](ClO4)2 (L1 = 2-(2-(tri-fluoromethyphenyl))-imidazo [4,5f][1–10]phenanthroline (1) and [Ru(phen)2(L2-(CH2)4-eria)](ClO4)2 (L2 = 2-(4-(tri-fluoromethyphenyl))-imidazo [4,5f][1,10]phenanthroline (2), have been synthesized and investigated as a potential G-quadruplex(G4) DNA stabilizer. Both complexes, especially 2, can bind to c-myc G4 DNA with high affinity by electronic spectra, and the binding constant calculated for 1 and 2 is about 15.1 and 2.05 × 107 M−1, respectively. This was further confirmed by the increase in fluorescence intensity for both complexes. Moreover, the positive band at 265 nm in the CD spectra of c-myc G4 DNA decreased treated with 2, indicating that 2 may bind to c-myc G4 DNA through extern groove binding mode. Furthermore, fluorescence resonance energy transfer (FRET) assay indicated that the melting point of c-myc G4 DNA treated with 1 and 2 increased 15.5 and 16.5 °C, respectively. Finally, molecular docking showed that 1 can bind to c-myc G4 DNA in the extern groove formed by base pairs G7–G9 and G22–A24, and 2 inserts into the small groove of c-myc G4 DNA formed by base pairs T19–A24. In summary, these ruthenium(II) complexes, especially 2, can be developed as potential c-myc G4 DNA stabilizers and will be exploited as potential anticancer agents in the future.
Vaccinium Species (Ericaceae): Phytochemistry and Biological Properties of Medicinal Plants
Authors: Martău Gheorghe Adrian , Bernadette-Emőke Teleky , Odocheanu Răzvan , Soporan Dacian Andrei , Bochiș Mihai , Simon Elemer , Vodnar Dan Cristian
Published: February 2023

The Vaccinium L. (Ericaceae) genus consists of a globally widespread and diverse genus of around 4250 species, of which the most valuable is the Vaccinioidae subfamily. The current review focuses on the distribution, history, bioactive compounds, and health-related effects of three species: cranberry, blueberry, and huckleberry. Several studies highlight that the consumption of Vaccinium spp. presents numerous beneficial health-related outcomes, including antioxidant, antimicrobial, anti-inflammatory, and protective effects against diabetes, obesity, cancer, neurodegenerative diseases and cardiovascular disorders. These plants’ prevalence and commercial value have enhanced in the past several years; thus, the generated by-products have also increased. Consequently, the identified phenolic compounds found in the discarded leaves of these plants are also presented, and their impact on health and economic value is discussed. The main bioactive compounds identified in this genus belong to anthocyanins (cyanidin, malvidin, and delphinidin), flavonoids (quercetin, isoquercetin, and astragalin), phenolic acids (gallic, p-Coumaric, cinnamic, syringic, ferulic, and caffeic acids), and iridoids.
Potential Treatment of Dermatophyte Trichophyton rubrum in Rat Model Using Topical Green Biosynthesized Silver Nanoparticles with Achillea santolina Extract
Authors: Abdallah Basem M. , Rajendran Peramaiyan , Ali Enas M.
Published: February 2023

Trichophyton rubrum is the most common dermatophyte, and can cause cutaneous infections in humans and animals (dermatophytosis). In this study, we investigated the anti-dermatophytic potential of green synthesized silver nanoparticles using Achillea santolina extract (AS-AgNPs) in an in vitro and in vivo rat model of dermal T. rubrum dermatophytosis (TRD). The green synthesis of AS-AgNPs was performed using A. santolina extract and characterized by UV-VIS spectroscopy, zeta potential, imaging (transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and Energy dispersive X-ray analysis (EDX). The antifungal activity of AS-AgNPs was determined by the broth microdilution method, conidial germination, and hyphal growth inhibition. TEM and SEM were used to study the mode of the antifungal action of AS-AgNPs. AS-AgNPs inhibited the growth of T. rubrum with an MIC of 128 μg/mL, and suppressed the conidial germination and hyphal growth by 55.3% 84.6%, respectively. AS-AgNPs caused modified mycelial structures, increased cell membrane permeability, and cell wall damage. AS-AgNPs significantly increase the permeability of the fungal membrane, as revealed by reducing ergosterol biosynthesis. An increase in the intracellular ROS and the induction of apoptosis were also observed during AS-AgNP treatment. In addition, AS-AgNPs reduced the cell wall integrity, as shown by the reduction in the β-(1,3)-d-glucan synthase and chitin synthase activities. AS-AgNPs showed very low toxicity on primary human dermal fibroblasts (HDF) at the MIC. The topical treatment of the infected skin in the TRD rat model with AS-AgNPs showed a significant reduction in the fugal burden after 7 days and a complete clearance of fungal conidia, with a high recovery of epidermal and dermal structures after 14 days, compared to control rats. Interestingly, AS-AgNPs significantly attenuated the infiltrated inflammatory cells, in association with reducing the tissue proinflammatory cytokines including TNF-α, IL-1, IL-6, MOP and IL-17. In conclusion, our data prove AS-AgNPs to be a novel green topical therapy for dermatophytosis caused by T. rubrum.
The Mechanism of Metal-Containing Formate Dehydrogenases Revisited: The Formation of Bicarbonate as Product Intermediate Provides Evidence for an Oxygen Atom Transfer Mechanism
Authors: Kumar Hemant , Khosraneh Maryam , Bandaru Siva S. M. , Schulzke Carola , Leimkühler Silke
Published: February 2023

Mo/W-containing formate dehydrogenases (FDH) catalyzed the reversible oxidation of formate to carbon dioxide at their molybdenum or tungsten active sites. While in the reaction of formate oxidation, the product is CO2, which exits the active site via a hydrophobic channel; bicarbonate is formed as the first intermediate during the reaction at the active site. Other than what has been previously reported, bicarbonate is formed after an oxygen atom transfer reaction, transferring the oxygen from water to formate and a subsequent proton-coupled electron transfer or hydride transfer reaction involving the sulfido ligand as acceptor.
Multiple Effects of High Surface Area Hollow Nanospheres Assembled by Nickel Cobaltate Nanosheets on Soluble Lithium Polysulfides
Authors: Pu Jun , Zhu Xiaomei , Wang Jie , Yu Shaomeng
Published: February 2023

Inhibiting the shuttle effect of soluble polysulfides and improving slow reaction kinetics are key factors for the future development of Li–S batteries. Herein, edelweiss shaped NiCo2O4 hollow nanospheres with a high surface area were prepared by a simple template method to modify the separator to realize multiple physical constraints and strong chemical anchoring on the polysulfides. On one hand, the good electrolyte wettability of NiCo2O4 promoted the migration of Li-ions and greatly improved the dynamics. On the other hand, mesoporous NiCo2O4 nanomaterials provided many strong chemical binding sites for loading sulfur species. The hollow structure also provided a physical barrier to mitigate the sulfur species diffusion. Therefore, the modified separator realized multiple physical constraints and strong chemical anchoring on sulfur species. As a result, the sulfur cathode based on this composite separator showed significantly enhanced electrochemical performance. Even at 4 C, a high capacity of 505 mAh g−1 was obtained, and about 80.6% could be retained after 300 cycles.
A Possible Natural and Inexpensive Substitute for Lapis Lazuli in the Frederick II Era: The Finding of Haüyne in Blue Lead-Tin Glazed Pottery from Melfi Castle (Italy)
Authors: Mangone Annarosa , Caggiani Maria Cristina , Forleo Tiziana , Giannossa Lorena Carla , Acquafredda Pasquale
Published: February 2023

The blue color of glass and ceramic glazes produced in Apulia and Basilicata (Southern Italy) between the 13th and 14th centuries and connected to the Norman-Swabian Emperor Frederick II, has been, for a long time, under archaeometric investigation. On the one hand, it has usually been associated with lapis lazuli, due to the finding of the polysulphide blue chromophores typical of lazurite. Moreover, the observation that the mineral haüyne, which belongs to the sodalite group as well as lazurite, can be blue and/or can gain a blue color after heating, due to the same chromophores, has caused this automatic attribution to be questioned, and also considering that the mineral is characteristic of the rock haüynophyre of Melfi (Potenza, Southern Italy), a location of interest for glass and pottery findings. In this paper, for the first time, several haüyne crystals were found in the blue glaze of a ceramic dish found at Melfi Castle, leading to the hypothesis that, in this case, the local haüyne-bearing source could have been used as the coloring raw material. The discovery was possible thanks to SEM-EDS and Raman analyses that, respectively, highlighted the typical numerous presence of very fine sulphur-based inclusions in the crystals and the characteristic Raman signal of blue haüyne. This study was also focused on the composition of the crystals inclusions, aided by SEM-EDS and Raman maps, since the original very fine pyrrhotite was transformed into Cu and Pb phases (copper sulphates, copper sulphides, and lead oxide) due to reactions with cations that had mobilized from the glaze, while the migration of Si from the glass allowed the transformation of the rim of the haüyne, a silica-undersaturated mineral, into a corona of small euhedral and neomorphic Pb-rich feldspars, a silica-saturated phase.
Experimental, Spectroscopic, and Computational Insights into the Reactivity of “Methanal” with 2-Naphthylamines
Authors: Havlík Martin , Navrátilová Tereza , Drozdová Michaela , Tatar Ameneh , Lanza Priscila A. , Dusso Diego , Moyano Elizabeth Laura , Chesta Carlos A. , Vera Domingo Mariano A. , Dolenský Bohumil
Published: February 2023

The reactions of 2-naphthylamine and methyl 6-amino-2-naphthoate with formalin and paraformaldehyde were studied experimentally, spectrally, and by quantum chemical calculations. It was found that neither the corresponding aminals nor imines were formed under the described conditions but could be prepared and spectrally characterized at least in situ under modified conditions. Several of the previously undescribed intermediates and by-products were isolated or at least spectrally characterized. First principle density functional theory (DFT) calculations were performed to shed light on the key aspects of the thermochemistry of decomposition and further condensation of the corresponding aminals and imines. The calculations also revealed that the electrophilicity of methanal was significantly greater than that of ordinary oxo-compounds, except for perfluorinated ones. In summary, methanal was not behaving as the simplest aldehyde but as a very electron-deficient oxo-compound.
Genetically Engineering Escherichia coli to Produce Xylitol from Corncob Hydrolysate without Lime Detoxification
Authors: Yuan Xinsong , Cao Jiyun , Wang Rui , Han Yu , Zhu Jinmiao , Lin Jianping , Yang Lirong , Wu Mianbin
Published: February 2023

Before fermentation with hemicellulosic hydrolysate as a substrate, it is generally necessary to detoxify the toxic substances that are harmful to microorganism growth. Cyclic AMP receptor protein (CRP) is a global regulator, and mutation of its key sites may have an important impact on E. coli virulence tolerance. Using corncob hydrolysate without ion-exchange or lime detoxification as the substrate, shake flask fermentation experiments showed that CRP mutant IS5-dG (I112L, T127G, A144T) produced 18.4 g/L of xylitol within 34 h, and the OD600 was 9.7 at 24 h; these values were 41.5% and 21.3% higher than those of the starting strain, IS5-d, respectively. This mutant produced 82 g/L of xylitol from corncob hydrolysate without ion-exchange or lime detoxification during fed-batch fermentation in a 15-L bioreactor, with a productivity of 1.04 g/L/h; these values were 173% and 174% higher than the starting strain, respectively. To our knowledge, this is the highest xylitol concentration and productivity produced by microbial fermentation using completely non-detoxified hemicellulosic hydrolysate as the substrate to date. This study also showed that alkali neutralization, high temperature sterilization, and fermentation of the hydrolysate had important effects on the xylose loss rate and xylitol production.
Suppression of Macrophage Activation by Sodium Danshensu via HIF-1α/STAT3/NLRP3 Pathway Ameliorated Collagen-Induced Arthritis in Mice
Authors: Wu Danbin , Xu Jia , Jiao Wei , Liu Lijuan , Yu Jiahui , Zhang Mingying , Chen Guangxing
Published: February 2023

It is still a clinical challenge to sustain the remission of rheumatoid arthritis (RA); thus, identifying more effective and safer agents for RA treatment remains an urgent demand. We investigated the anti-arthritic activity and potential mechanism of action of sodium Danshensu (SDSS), a structurally representative water-soluble derivative of Danshen, on collagen-induced arthritis (CIA) mice. Our results showed that paw edema, synovium hyperplasia, bone destruction, and the serum levels of both IL-1β and IL-6 were ameliorated by SDSS (40 mg/kg·d) in CIA mice. In addition, there was no difference between SDSS and methotrexate (MTX, 2 mg/kg·3d) treatment in the above indicators. Further mechanism studies illustrated that SDSS inhibited IL-1β secretion by downregulating the HIF-1α/STAT3/NLRP3 pathway in macrophages. On the other hand, HIF-1α accumulation and HIF-1α/STAT3/NLRP3 pathway activation by IOX4 stimulation reduced the therapeutic effect of SDSS. These findings demonstrate that SDSS displays anti-arthritic activity in CIA mice and prevents proinflammatory cytokines secretion in macrophages by suppressing the HIF-1α/STAT3/NLRP3 pathway.
Search and Identification of Amyloid Proteins
Authors: Belashova Tatyana A. , Valina Anna A. , Sysoev Evgeniy I. , Velizhanina Maria E. , Zelinsky Andrew A. , Galkin Alexey P.
Published: February 2023

Amyloids are fibrillar proteins with a cross-β structure. Pathological amyloids are associated with the development of a number of incurable diseases, while functional amyloids regulate vital processes. The detection of unknown amyloids in living objects is a difficult task, and therefore the question of the prevalence and biological significance of amyloids remains open. We present a description of two methods, the combination of which makes it possible to find and identify amyloid proteins in the proteome of various organisms. The method of proteomic screening for amyloids allows the detection of the proteins that form SDS-resistant aggregates. SDS resistance is a general feature of amyloid fibrils. Protein aggregates resistant to SDS treatment can be collected by ultracentrifugation and further identified by mass spectrometry. However, in addition to amyloids, SDS-resistant aggregates contain some non-amyloid proteins. To test the amyloid properties of proteins identified by proteomic screening, we developed the method of fibril immunoprecipitation followed by Congo red staining and birefringence analysis. The methods of proteomic screening and immunoprecipitation of fibrillar proteins have been successfully tested and applied for the identification of amyloid proteins in yeast and vertebrates.