Porphyrin Catecholate Iron-Based Metal–Organic Framework for Efficient Visible Light-Promoted One-Pot Tandem C–C Couplings

Introduction of metal–organic frameworks (MOFs) beyond metal-carboxylate series and their applications are still challenging. An innovative porous porphyrin catecholate iron-based MOF (PorphCat-Fe) with a Brunauer–Emmett–Teller (BET) surface area of 700 m2 g–1 has been designed and synthesized through solvothermal self-assembling porphyrin catecholate linkers and iron(II) chloride as a cheap and earth-abundant node precursor. The structure was then evaluated with various techniques and utilized as an efficient and stable heterogeneous material for domino one-pot selective benzyl alcohol oxidation/Knoevenagel condensation reaction under visible LED light irradiation. The photocatalytic performance was remarkably improved as compared to individual components, affording excellent product yields (91%) with almost quantitative transformation of benzyl alcohol. The combination of Fe(III)-Lewis acidic sites and free-base porphyrin photosensitizers within the porous solid material make PorphCat-Fe able to show superior catalytic activity for this transformation. In addition, the MOF can easily accommodate the starting materials inside its mesopores and, thereby, make them easily accessible to active sites. This is an unusual example of an all-in-one noble metal-free bio-inspired supramolecular chemistry for an advanced organic transformation without the need of any chemical additive or further structural modification using only visible LED light conservation

Time-to-event overall survival prediction in glioblastoma multiforme patients using magnetic resonance imaging radiomics

Purpose: Glioblastoma Multiforme (GBM) represents the predominant aggressive primary tumor of the brain with short overall survival (OS) time. We aim to assess the potential of radiomic features in predicting the time-to-event OS of patients with GBM using machine learning (ML) algorithms. Materials and methods: One hundred nineteen patients with GBM, who had T1-weighted contrast-enhanced and T2-FLAIR MRI sequences, along with clinical data and survival time, were enrolled. Image preprocessing methods included 64 bin discretization, Laplacian of Gaussian (LOG) filters with three Sigma values and eight variations of Wavelet Transform. Images were then segmented, followed by the extraction of 1212 radiomic features. Seven feature selection (FS) methods and six time-to-event ML algorithms were utilized. The combination of preprocessing, FS, and ML algorithms (12 × 7 × 6 = 504 models) was evaluated by multivariate analysis. Results: Our multivariate analysis showed that the best prognostic FS/ML combinations are the Mutual Information (MI)/Cox Boost, MI/Generalized Linear Model Boosting (GLMB) and MI/Generalized Linear Model Network (GLMN), all of which were done via the LOG (Sigma = 1 mm) preprocessing method (C-index = 0.77). The LOG filter with Sigma = 1 mm preprocessing method, MI, GLMB and GLMN achieved significantly higher C-indices than other preprocessing, FS, and ML methods (all p values &lt; 0.05, mean C-indices of 0.65, 0.70, and 0.64, respectively). Conclusion: ML algorithms are capable of predicting the time-to-event OS of patients using MRI-based radiomic and clinical features. MRI-based radiomics analysis in combination with clinical variables might appear promising in assisting clinicians in the survival prediction of patients with GBM. Further research is needed to establish the applicability of radiomics in the management of GBM in the clinic.</p

Effect Long-Term Management System on Soil Weed Seed Bank

Long-term monoculture has a de-stroying impact on plant production, while crop rotation is known as a more eco-friendly approach as provides diversification in crop management systems, modifies intensive pressure on the agricultural ecosystem, utilizes various soil horizons, and prevents the establishment of specific pests and weeds. The aim of his research was to answer: How management system over 50 years of specific continuous crop management programs (crop rotation and fertilization) effect on weed populations? This study was conducted in the experimental site of the Institute of Field and Vegetable Crops of “Plodoredi”, Rimski Šančevi, Novi Sad, Serbia. It has been estimated three monocultures of maize, wheat and soybean, 2-year crop rotation (winter wheat-maize) with and without chemical fertilizer and 3–year crop rotation (winter wheat-soybean-maize) with and without chemical fertilizer and manure. Soil samples were taken six times from 2014 to 2017 prior to sowing and after harvesting each year. Weed seeds were extracted from soils and identified and counted by species. Mixed model analysis was used to determine the effect of the crop sequence and fertilizers on weed seed bank. To compare the strength of the treatment, it calculated the log-worth with their P-values. Upon the data of a long term experiment of crop rotation, could approve that crop rotations with more crops in the sequence are significantly effective in maintaining weed population. Therefore, will be a more sustainable crop production, chemical fertilizers would imbalance the plant population diversity and manures with high number of weed seeds have potentials to totally vanish crop rotation effects. Mixed model analysis suggests that on over 50 years of the management practices crop sequence × fertilizer interaction had the highest effect (log-worth = 64.7), followed by the triple interactions between crop sequence × fertilizer × soil depth (log-worth = 30.5). The number of seeds in soil significantly decreased from surface layer to deep soil. The crop sequence efficiency in decreasing weed seed bank was highly dependent on the fertilizer management, as with chemical fertilizer, the three years crop rotations had significantly lower seed bank, while with manure, the effect of crop rotations was eliminated

Crop rotation influence on vertical weed seed bank

Soil weed seed bank represents a latent plant community, so, the knowledge of vertical distribution and number of seeds in soil profile is one of the reliable ways to prepare the adequate weed control strategy. It is believed that the crop rotation is one of the most important agrotechnical measures which, in interaction with weed control, impact both size and composition of the weed seed bank. In a long-term stationary experiment “Plodoredi” at the Institute of Field and Vegetable Crops, Novi Sad, Serbia (N 45° 19', E 19° 50') a weed seed bank in wheat monoculture, two year crop rotation (winter wheat – maize) and three year crop rotation (winter wheat – soybean – maize) has been estimated. Based on a three-year successive soil sampling in depth of 0–15, 15–30 and 30–40 cm and by applying the method of physical extraction of seed it has been established that in all three crop systems the seeds are distributed in the way that the layer of 0-15 cm had most seeds. The abundance decreased gradually with the increase in depth

Which methods are the most reliable for predict weed seed bank?

The primary aim of the study was to estimate the weed seed bank in different management systems. Research on this topic is modestly and there are great variability in the results with similarly set experimental conditions, because of using different methods. Therefore, it was decided to use square method and to compare two methods for estimating weed seed bank: physical extraction of seed and seedling emergence method. The research was performed at the stationary long-term experiment "Plodoredi" of the Institute of Field and Vegetables Crops in Novi Sad. During three years and 6 assessment and 2-year crop rotation (winter wheat-maize) with standard application of mineral fertilizer 100 kg ha-1 N was monitored. During the first year (2014), method physical extraction of seed gave an insight that 20.100 seeds per m2, which belong to 18 weed species, persist in the entire examined soil layer (0-40 cm). Using the seedling emergence method, it was estimated only 4.625 seeds per m2, which originate from 5 weed species. During the last assessment (2017), the physical extraction, although more complicated, indicated that there were 27.075 seeds per m2 in the examined layer, i.e. 20 weed species

Model za simulaciju procene rezerve semena korovskih biljaka u zemljištu

Rezerve semena korovskih biljaka u zemljištu sa jedne strane predstavljaju stalni izvor zakorovljenosti, dok sa druge imaju ulogu u održavanju stabilnosti ekosistema i biodiverziteta. Malobrojna istraživanja na ovu temu su pokazala veliku varijabilnost u rezultatima, u sličnim eksperimentalnim uslovima, ali pri korišćenju različitih metoda. Stoga ciljevi u ovom istraživanja su bili odabir adekvatne i precizne metode za procenu rezerve semena korovskih biljaka i pravljenje pouzdanog modela za prognoziranje dinamike pojave korovskih populacija. Istraživanja su izvedena na oglednom polju Instituta za ratarstvo i povrtarstvo u Novom Sadu (N 45°19', E 19°50') u okviru dugogodišnjeg stacioniranog ogleda „Plodoredi”, koji se smatra jednim od najstarijih eksperimenata ovog tipa na prostoru jugoistočne Evrope. U ogledu se ispitivao uticaj sistema gajenja useva na sastav rezervi semena korovskih biljaka, a potom se upoređivao trоpoljni plodored (ozima pšenica-soja-kukuruz) sa monokulturom ozime pšenice. U obe varijante primenjen je isti sistem đubrenja i to 100 kg/ha N (50 kg/ha u jesen pred osnovnu obradu i 50 kg/ha u proleće u prihrani). Za uzorkovanje zemljišta primenjen je „metod kvadrata”, kao pouzdaniji u odnosu na šahovski tip i uzorkovanje po dijagonali koji se u praksi češće koriste. Procena rezerve semena korovskih biljaka urađena je primenom dva metodološka postupka: fizička ekstrakcija semena i naklijavanje zemljišnih uzoraka

Impact of feature harmonization on radiogenomics analysis:Prediction of EGFR and KRAS mutations from non-small cell lung cancer PET/CT images

Objective: To investigate the impact of harmonization on the performance of CT, PET, and fused PET/CT radiomic features toward the prediction of mutations status, for epidermal growth factor receptor (EGFR) and Kirsten rat sarcoma viral oncogene (KRAS) genes in non-small cell lung cancer (NSCLC) patients. Methods: Radiomic features were extracted from tumors delineated on CT, PET, and wavelet fused PET/CT images obtained from 136 histologically proven NSCLC patients. Univariate and multivariate predictive models were developed using radiomic features before and after ComBat harmonization to predict EGFR and KRAS mutation statuses. Multivariate models were built using minimum redundancy maximum relevance feature selection and random forest classifier. We utilized 70/30% splitting patient datasets for training/testing, respectively, and repeated the procedure 10 times. The area under the receiver operator characteristic curve (AUC), accuracy, sensitivity, and specificity were used to assess model performance. The performance of the models (univariate and multivariate), before and after ComBat harmonization was compared using statistical analyses. Results: While the performance of most features in univariate modeling was significantly improved for EGFR prediction, most features did not show any significant difference in performance after harmonization in KRAS prediction. Average AUCs of all multivariate predictive models for both EGFR and KRAS were significantly improved (q-value &lt; 0.05) following ComBat harmonization. The mean ranges of AUCs increased following harmonization from 0.87-0.90 to 0.92-0.94 for EGFR, and from 0.85-0.90 to 0.91-0.94 for KRAS. The highest performance was achieved by harmonized F_R0.66_W0.75 model with AUC of 0.94, and 0.93 for EGFR and KRAS, respectively. Conclusion: Our results demonstrated that regarding univariate modelling, while ComBat harmonization had generally a better impact on features for EGFR compared to KRAS status prediction, its effect is feature-dependent. Hence, no systematic effect was observed. Regarding the multivariate models, ComBat harmonization significantly improved the performance of all radiomics models toward more successful prediction of EGFR and KRAS mutation statuses in lung cancer patients. Thus, by eliminating the batch effect in multi-centric radiomic feature sets, harmonization is a promising tool for developing robust and reproducible radiomics using vast and variant datasets.</p

A Pyridyltriazol Functionalized Zirconium Metal-Organic Framework for Selective and Highly Efficient Adsorption of Palladium

[EN] This work reports the synthesis of pyridyltriazol-functionalized UiO-66 (UiO stands for University of Oslo), namely, UiO-66-Pyta, from UiO-66-NH2 through three postsynthetic modification (PSM) steps. The good performance of the material derives from the observation that partial formylation (similar to 21% of -NHCHO groups) of H2BDC-NH2 by DMF, as persistent impurity, takes place during the synthesis of the UiO-66-NH2. Thus, to enhance material performance, first, the as-synthesized UiO-66-NH2 was deformylated to give pure UiO-66-NH2. Subsequently, the pure UiO-66-NH2 was converted to UiO-66-N-3 with a nearly complete conversion (similar to 95%). Finally, the azide-alkyne[3+2]-cycloaddition reaction of 2-ethynylpyridine with the UiO-66-N-3 gave the UiO-66-Pyta. The porous MOF was then applied for the solid-phase extraction of palladium ions from an aqueous medium. Affecting parameters on extraction efficiency of Pd(II) ions were also investigated and optimized. Interestingly, UiO-66-Pyta exhibited selective and superior adsorption capacity for Pd(II) with a maximum sorption capacity of 294.1 mg.g(-1) at acidic pH (4.5). The limit of detection (LOD) was found to be 1.9 mu g L-1. The estimated intra- and interday precisions are 3.6 and 1.7%, respectively. Moreover, the adsorbent was regenerated and reused for five cycles without any significant change in the capacity and repeatability. The adsorption mechanism was described based on various techniques such as FT-IR, PXRD, SEM/EDS, ICP-AES, and XPS analyses as well as density functional theory (DFT) calculations. Notably, as a case study, the obtained UiO-66-Pyta after palladium adsorption, UiO-66-Pyta-Pd, was used as an efficient catalyst for the Suzuki-Miyaura cross-coupling reaction.Authors gratefully acknowledge the financial support for this work from the Politecnica de Valencia, Valencia, Spain. Also, financial support by the University of Zabol is gratefully acknowledged (grant nos. 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How Do Long Term Crop Rotations Influence Weed Populations: Exploring the Impacts of More than 50 Years of Crop Management in Serbia

Crop rotation is known as an eco-friendlier approach, as provides diversification in crop management systems, modifies intensive pressure on the agricultural ecosystem, utilizes various soil horizons, and prevents the establishment of specific pests and weeds. We set out here a study on the farms that have been managed over 50 years of specific continuous crop management programs. The experimental treatments were in a different management system: monoculture of maize, winter wheat, and soybean, 2-year crop rotation (winter wheat–maize) with and without chemical fertilizer, and 3-year crop rotation (winter wheat–soybean–maize) with and without chemical fertilizer and manure. We took soil samples six times from 2014 to 2017 prior to sowing and after harvesting each year. Weed seeds were extracted from soils and identified and counted by species. We, upon the data of a long term experiment of crop rotation, could conclude that crop rotations with more crops in the sequence are significantly effective in maintaining weed populations, a low-input crop production could reach a constant low population below an important damaging density, and therefore will be a more sustainable crop production while chemical fertilizers would change the soil’s chemical and structure and imbalance the plant population diversity and manures with high weed seed infestations have the potential to totally eradicate crop rotation effects, Therefore, clean manures or compost are highly recommended