Predicting the catalytic activities of transition metal (Cr, Fe, Co, Ni) complexes towards ethylene polymerization by machine learning.

The study aims to execute machine learning (ML) method for building an intelligent prediction system for catalytic activities of a relatively big dataset of 1056 transition metal complex precatalysts in ethylene polymerization. Among 14 different algorithms, the CatBoost ensemble model provides the best prediction with the correlation coefficient (R2 ) values of 0.999 for training set and 0.834 for external test set. The interpretation of the obtained model indicates that the catalytic activity is highly correlated with number of atom, conjugated degree in the ligand framework, and charge distributions. Correspondingly, 10 novel complexes are designed and predicted with higher catalytic activities. This work shows the potential application of the ML method as a high-precision tool for designing advanced catalysts for ethylene polymerization.

Catalytic Activity of 2-Imino-1,10-phenthrolyl Fe/Co Complexes via Linear Machine Learning.

In anticipation of the correlations between catalyst structures and their properties, the catalytic activities of 2-imino-1,10-phenanthrolyl iron and cobalt metal complexes are quantitatively investigated via linear machine learning (ML) algorithms. Comparatively, the Ridge Regression (RR) model has captured more robust predictive performance compared with other linear algorithms, with a correlation coefficient value of R2= 0.952 and a cross-validation value of Q2= 0.871. It shows that different algorithms select distinct types of descriptors, depending on the importance of descriptors. Through the interpretation of the RR model, the catalytic activity is potentially related to the steric effect of substituents and negative charged groups. This study refines descriptor selection for accurate modeling, providing insights into the variation principle of catalytic activity.

Correlation between serum IGF-1 and EGF levels and neuropsychiatric and cognitive in Parkinson's disease patients.

BACKGROUND: Insulin-like growth factor 1 (IGF-1) and epidermal growth factor (EGF) exert neuroprotective effects in Parkinson's disease (PD). To date, studies on the relationships between serum IGF-1 and EGF levels and nonmotor symptoms in PD patients have been rare. METHODS: A Siemens automatic chemical analyzer was used to determine serum IGF-1 levels, and enzyme-linked immunosorbent assay was used to detect serum EGF levels in 100 healthy controls and 100 PD patients, including those in the early (n = 49) and middle-late (n = 51) stage of the disease. Evaluation of motor symptoms and nonmotor symptoms in PD patients was assessed by the associated scales. RESULTS: Serum IGF-1 and EGF levels were higher in PD patients than in healthy controls, and serum IGF-1 and EGF levels were higher in early stage PD patients than in middle-late stage PD patients. Serum IGF-1 levels were significantly negatively correlated with anxiety, depression, and cognitive dysfunction; serum EGF levels were significantly negatively correlated with cognitive dysfunction. Combining IGF-1 and EGF in the diagnosis of PD was more valuable than using a single factor in the diagnosis. CONCLUSIONS: This study shows that serum IGF-1 levels were correlated with the nonmotor symptoms of anxiety, depression, and cognitive dysfunction and that EGF levels were correlated with cognitive dysfunction. The combination of IGF-1 and EGF increased the value for a PD diagnosis. This is the first report of the simultaneous detection of IGF-1 and EGF levels to explore the correlation with nonmotor symptoms of PD.

N,N-Bis(2,4-Dibenzhydryl-6-cycloalkylphenyl)butane-2,3-diimine-Nickel Complexes as Tunable and Effective Catalysts for High-Molecular-Weight PE Elastomers.

Four examples of N,N-bis(aryl)butane-2,3-diimine-nickel(II) bromide complexes, [ArN=C(Me)-C(Me)=NAr]NiBr2 (where Ar = 2-(C5H9)-4,6-(CHPh2)2C6H2 (Ni1), Ar = 2-(C6H11)-4,6-(CHPh2)2C6H2 (Ni2), 2-(C8H15)-4,6-(CHPh2)2C6H2 (Ni3) and 2-(C12H23)-4,6-(CHPh2)2C6H2 (Ni4)), disparate in the ring size of the ortho-cycloalkyl substituents, were prepared using a straightforward one-pot synthetic method. The molecular structures of Ni2 and Ni4 highlight the variation in the steric hindrance of the ortho-cyclohexyl and -cyclododecyl rings exerted on the nickel center, respectively. By employing EtAlCl2, Et2AlCl or MAO as activators, Ni1-Ni4 displayed moderate to high activity as catalysts for ethylene polymerization, with levels falling in the order Ni2 (cyclohexyl) > Ni1 (cyclopentyl) > Ni4 (cyclododecyl) > Ni3 (cyclooctyl). Notably, cyclohexyl-containing Ni2/MAO reached a peak level of 13.2 × 106 g(PE) of (mol of Ni)-1 h-1 at 40 °C, yielding high-molecular-weight (ca. 1 million g mol-1) and highly branched polyethylene elastomers with generally narrow dispersity. The analysis of polyethylenes with 13C NMR spectroscopy revealed branching density between 73 and 104 per 1000 carbon atoms, with the run temperature and the nature of the aluminum activator being influential; selectivity for short-chain methyl branches (81.8% (EtAlCl2); 81.1% (Et2AlCl); 82.9% (MAO)) was a notable feature. The mechanical properties of these polyethylene samples measured at either 30 °C or 60 °C were also evaluated and confirmed that crystallinity (Xc) and molecular weight (Mw) were the main factors affecting tensile strength and strain at break (εb = 353-861%). In addition, the stress-strain recovery tests indicated that these polyethylenes possessed good elastic recovery (47.4-71.2%), properties that align with thermoplastic elastomers (TPEs).

Low serum uric acid levels are associated with the nonmotor symptoms and brain gray matter volume in Parkinson's disease.

BACKGROUND: Uric acid (UA) plays a protective role in Parkinson's disease (PD). To date, studies on the relationship between serum UA levels and nonmotor symptoms and brain gray matter volume in PD patients have been rare. METHODS: Automated enzymatic analysis was used to determine serum UA levels in 68 healthy controls and 88 PD patients, including those at the early (n = 56) and middle-late (n = 32) stages of the disease. Evaluation of motor symptoms and nonmotor symptoms in PD patients was assessed by the associated scales. Image acquisition was performed using a Siemens MAGNETOM Prisma 3 T MRI scanner. RESULTS: Serum UA levels in early stage PD patients were lower than those in healthy controls, and serum UA levels in the middle-late stage PD patients were lower than those in the early stage PD patients. Serum UA levels were significantly negatively correlated with the disease course, dysphagia, anxiety, depression, apathy, and cognitive dysfunction. ROC assessment confirmed that serum UA levels had good predictive accuracy for PD with dysphagia, anxiety, depression, apathy, and cognitive dysfunction. Furthermore, UA levels were significantly positively correlated with gray matter volume in whole brain. CONCLUSIONS: This study shows that serum UA levels were correlated with the nonmotor symptoms of dysphagia, anxiety, depression, apathy, and cognitive dysfunction and the whole-brain gray matter volume. That is the first report examining the relationships between serum UA and clinical manifestations and imaging features in PD patients.

Plasma arylsulfatase A levels are associated with cognitive function in Parkinson's disease.

BACKGROUND: Arylsulfatase A (ARSA), a lysosomal enzyme, has been shown to inhibit the aggregation and propagation of α-synuclein (α-syn) through its molecular chaperone function. The relationship between ARSA levels and Parkinson's disease (PD) in the Chinese Han population remains controversial, and few quantitative research studies have investigated the relationship between plasma ARSA levels and PD. OBJECTIVES: The purpose of this study was to investigate the relationships between ARSA levels and cognitive function in PD patients and to evaluate the association of ARSA and α-syn levels with nonmotor symptoms. METHODS: Enzyme-linked immunosorbent assay (ELISA) was used to measure the plasma ARSA and α-syn levels in 50 healthy controls, 120 PD patients (61 PD patients with no cognitive impairment (PD-NCI) and 59 PD patients with cognitive impairment (PD-CI)). Motor symptoms and nonmotor symptoms (cognitive function, Unified Parkinson's Disease Rating Scale (UPDRS) score, depression, anxiety, constipation, olfactory dysfunction, sleep disruption, and other symptoms) were assessed with the relevant scales. The Kruskal-Wallis H test was used for comparison between groups, and Pearson/Spearman analysis was used for correlation analysis. RESULTS: The plasma ARSA concentrations were lower in the PD-CI group than in the PD-NCI group. The plasma α-syn levels in the PD-CI group were higher than those in the healthy control group, and the plasma ARSA levels were correlated with the Mini-Mental State Examination (MMSE scores) and Hoehn and Yahr (H-Y) stage. CONCLUSION: We used a quantitative assessment method to show that low plasma ARSA levels and high α-syn levels are related to cognitive impairment in PD patients. Plasma ARSA levels gradually decrease with PD progression.

Effects of frailty on postoperative clinical outcomes of aneurysmal subarachnoid hemorrhage: results from the National Inpatient Sample database.

BACKGROUND: This study aimed to investigate the potential effect of preoperative frailty on postoperative clinical outcomes of patients with aneurysmal subarachnoid hemorrhage (aSAH). METHODS: Data of patients aged 18 years and older who were diagnosed with subarachnoid hemorrhage or intracerebral hemorrhage, underwent aneurysm repair surgical intervention from 2005 to 2014. A retrospective database analysis was performed based on U.S. National Inpatient Sample (NIS) from 2005 to 2014. Frailty was determined using the Johns Hopkins Adjusted Clinical Groups (ACG) frailty-defining diagnoses indicator. Patients were stratified into frail and non-frail groups and the study endpoints were incidence of postoperative complications and related adverse clinical outcomes. RESULTS: Among 20,527 included aSAH patients, 2303 (11.2%) were frail and 18,224 (88.8%) were non-frail. Significant differences were found between frailty and non-frailty groups in the four clinical outcomes (all p < 0.05). Multivariate analysis showed that frailty was associated with significant higher risks of discharge to institutional care (aOR: 2.50, 95%CI: 2.10-2.97), tracheostomy or gastrostomy tube replacement (aOR: 4.41, 95%CI: 3.81-5.10) and postoperative complications (aOR: 3.29, 95%CI: 2.55-4.25) but a lower risk of death in hospital (aOR: 0.40, 95%CI: 0.33-0.49) as compared with non-frailty. Stratified analysis showed the impact of frailty on some of the outcomes were greater among patients younger than 65 years than their older counterparts. CONCLUSIONS: Frailty is significantly correlated with the increased risk of discharge to institutional care, tracheostomy or gastrostomy tube placement, and postoperative complications but with the reduced risk of in-hospital mortality outcomes after aneurysm repair. Frailty seems to have greater impact among younger adults than older ones. Baseline frailty evaluation could be applied to risk stratification for aSAH patients who were undergoing surgery.

Combined strategy of knowledge-based rule selection and historical data percentile-based range determination to improve an autoverification system for clinical chemistry test results.

BACKGROUND: Current autoverification, which is only knowledge-based, has low efficiency. Regular historical data analysis may improve autoverification range determination. We attempted to enhance autoverification by selecting autoverification rules by knowledge and ranges from historical data. This new system was compared with the original knowledge-based system. METHODS: New types of rules, extreme values, and consistency checks were added and the autoverification workflow was rearranged to construct a framework. Criteria for creating rules for extreme value ranges, limit checks, consistency checks, and delta checks were determined by analyzing historical Zhongshan laboratory data. The new system's effectiveness was evaluated using pooled data from 20 centers. Efficiency improvement was assessed by a multicenter process. RESULTS: Effectiveness was evaluated by the true positive rate, true negative rate, and overall consistency rate, as compared to manual verification, which were 77.55%, 78.53%, and 78.3%, respectively for the new system. The original overall consistency rate was 56.2%. The new pass rates, indicating efficiency, were increased by 19%-51% among hospitals. Further customization using individualized data increased this rate. CONCLUSIONS: The improved system showed a comparable effectiveness and markedly increased efficiency. This transferable system could be further improved and popularized by utilizing historical data from each hospital.

Antioxidant Effect of Taurine on Chronic Heat-Stressed Broilers.

The purpose of this study was to investigate the effects of taurine on blood indices of broilers with chronic heat stress and to provide theoretical basis for the application of taurine in the anti-chronic heat stress of broilers. In the test, 240 AA + broilers at 7 days of age were randomly divided into five groups: the normal temperature control group (24 ± 2 °C) in group C, the heat stress control group (34 ± 2 °C) in HS group, and the LTau, MTau, and HTau groups in heat under stress conditions, 0.5 g/L, 2 g/L, and 8 g/L taurine, were added to the drinking water, and each group was repeated three times. After 2 weeks of feeding at normal temperature, heat stress began. The test period was 4 weeks. Blood was collected at 6 h, 12 h, 7 d, 14 d, 21 d, and 28 d after heat stress, and serum was separated. The results showed that compared with the HS group, MTau significantly increased the total serum protein content (P < 0.05), but the other groups were not significantly different (P > 0.05). The MTau and HTau groups contained significantly lowered serum uric acid levels than the HS group (P < 0.05). At 7d and 14d, the LTau, MTau, and HTau groups all exhibited significantly increased T3 and T4 concentrations (P < 0.05). There was no significant difference between the groups at other times (P > 0.05). Compared with the HS group, the MTau group contained significantly reduced serum CK activity, LDH activity, AST activity, and ALT activity (P < 0.05). Compared with the LTau, MTau, and HTau groups, serum MDA content was significantly increased in the heat-stressed broilers (P < 0.05). MTau group contained significantly increased T-AOC, SOD, CAT, and GSH-PX levels (P < 0.05). The other groups were not significantly different (P > 0.05). Compared with group C, serum HSP60 and HSP70 levels were significantly elevated in the HS group (P < 0.05). Compared with the HS group, the LTau and MTau groups contained significantly increased serum HSP60 and HSP70 concentrations (P < 0.05), but the other groups were not significantly different (P > 0.05). In conclusion, taurine can alleviate the symptoms of chronic heat stress of broilers, regulate the metabolism of the body, and improve the antioxidant activity of the body.

Effects of Taurine on Serum Indexes of Broilers with Chronic Heat Stress.

The aim of this study was to investigate the effects of taurine on tissue injury, protein metabolism, and basal metabolism of broilers after chronic heat stress by detecting serum physiological and biochemical indices. In the test, 240 AA + broilers at 7 days of age were randomly divided into five groups: the normal temperature control group (24 ± 2 °C) in group C, the heat stress control group (34 ± 2 °C) in HS group, and the LTau, MTau, and HTau groups in heat under stress conditions, 0.5, 2, and 8 g/L taurine were added to the drinking water, and each group was repeated three times. After 2 weeks of feeding at normal temperature, heat stress began. The test period was 4 weeks. Blood was collected at 6 h, 12 h, 7 d, 14 d, 21 d, and 28 d after heat stress, and serum was separated. The results showed that compared with the HS group, the MTau group had significantly higher total serum protein content (P < 0.05), while the other groups were not significantly different (P > 0.05). The MTau and HTau groups had significantly lower serum uric acid levels than the HS group (P < 0.05). At 7d and 14d, the LTau, MTau, and HTau groups all showed significantly increased T3 and T4 concentrations (P < 0.05). There was no significant difference between the groups thereafter (P > 0.05). Compared with HS group, the MTau group contained significantly reduced serum CK activity, LDH activity, AST activity, and ALT activity (P < 0.05). In conclusion, the effects of taurine on tissue damage, protein metabolism, and basal metabolism of broilers after chronic heat stress were studied by measuring serum physiological and biochemical indices. To provide a theoretical basis for the application of taurine in acute heat-stressed broilers.

Unusual Effect of α-olefins as Chain Transfer Agents in Ethylene Polymerization over the Catalyst with Nonsymmetrical Bis(imino)pyridine Complex of Fe(II) and Modified Methylalumoxane (MMAO) Cocatalyst.

Ethylene polymerization with bis(imino)pyridlyiron precatalysts generally produces linear polyethylene (PE) even with the presence of α-olefins because α-olefins are not incorporated into polymeric products. Interestingly, α-olefins, such as hexene-1 or butene-1, have been found to act as effective chain transfer agents in the ethylene polymerization promoted by nonsymmetrical bis(imino)pyridyliron complexes with modified methylalumoxane (MMAO), resulting in higher catalytic activities with higher amounts of polymers with lower molecular weights, and, more importantly, narrower molecular weight distributions of the resultant polyethylenes (PE). This phenomenon confirms the assistance of α-olefins in the chain-termination reaction of iron-initiated polymerization and regeneration of the active species for further polymerization. Besides higher activities of the catalytic system, the formation of linear PE with trans-vinylene terminal groups and lower molecular weights are explained. The observation will provide a new pathway for enhancing catalytic activity and improving the quality of polyethylenes obtained by regulation of molecular weights and molecular weight distribution.

Catalytic Performance of Cobalt(II) Polyethylene Catalysts with Sterically Hindered Dibenzopyranyl Substituents Studied by Experimental and MLR Methods.

Given the great importance of cobalt catalysts supported by benchmark bis(imino)pyridine in the (oligo)polymerization, a series of dibenzopyran-incorporated symmetrical 2,6-bis(imino) pyridyl cobalt complexes (Co1-Co5) are designed and prepared using a one-pot template approach. The structures of the resulting complexes are well characterized by a number of techniques. After activation with either methylaluminoxane (MAO) or modified MAO (MMAO), the complexes Co1-Co4 are highly active for ethylene polymerization with a maximum activity of up to 7.36 × 106 g (PE) mol-1 (Co) h-1 and produced highly linear polyethylene with narrow molecular weight distributions, while Co5 is completely inactive under the standard conditions. Particularly, complex Co3 affords polyethylene with high molecular weights of 85.02 and 79.85 kg mol-1 in the presence of MAO and MMAO, respectively. The 1H and 13C NMR spectroscopy revealed the existence of vinyl end groups in the resulting polyethylene, highlighting the predominant involvement of the ß-H elimination reaction in the chain-termination process. To investigate the mechanism underlying the variation of catalytic activities as a function of substituents, multiple linear regression (MLR) analysis was performed, showing the key role of open cone angle (θ) and effective net charge (Q) on catalytic activity.

The Quantitative Influence of Coordinated Halogen Atoms on the Catalytic Performance of Bisiminoacenaphthylnickel Complexes in Ethylene Polymerization.

In experiments, nickel bromine complexes usually show a better catalytic performance in ethylene polymerization compared to their nickel chlorine analogues. Therefore, the present modeling study has been performed to investigate the effect of coordinated halogen atoms on the catalytic performances of two bisiminoacenaphthyl nickel systems, namely, Ni-Br and Ni-Cl. By using the multiple linear regression analysis (MLRA), the catalytic activity can be well predicted by the descriptors of effective net charge (Qeff ) and bite angle (ß), with correlation coefficient R2 values over 0.91. Meanwhile, the molecular weights of polyethylene are predicted by the descriptors of Qeff and open cone angle (θ). The calculated contributions of each descriptor show that the electronic effect is the predominant factor in Ni-Br system, while the steric effect becomes the dominant factor in Ni-Cl system. The different determined effect is expected to the main reason for the different catalytic performance between two Ni systems.

Effects of Chiral Molecule Modification on Surface Biosorption Behavior.

Antifouling materials have many important applications in biomedical devices and marine coating. Oligo(ethylene glycol) (OEG) or poly(ethylene glycol) (PEG) exhibit promising antifouling properties and are widely used in biomedical engineering. Chiral selection is an important phenomenon in biological processes. Because of the influence of steric hindrance, the modification of chiral molecules with different chirality at interfaces will affect the intermolecular interaction at the interfaces and lead to different structures of interfacial molecules. The difference of surface structures such as surface hydration structure would impact the adsorption of biomolecules on the surface, thus causing different varieties of cell adhesion and cell growth. In this study, the influence on surface hydration and surface cell adhesion of OEG self-assembled monolayers (SAMs) modified with cysteine showing different chirality are explored. The water structure at the interfaces of OEG/water in different conditions was probed with sum frequency generation vibrational spectroscopy (SFG-VS). The results show that the interfacial water structure can change significantly with either d-cysteine or l-cysteine modification on OEG. Water molecules are more ordered at the OEG/water interface under the d-cysteine modification on OEG SAMs, which improves the protein adsorption resistance of the surface. In contrast, l-cysteine modification would make the water less ordered at the OEG/protein solution interface and enhance the protein adsorption. Additionally, optical micrographs indicate that l-cysteine can significantly promote the OEG SAMs cell adhesion and growth, while d-cysteine exhibits an inhibitory effect, which is consistent with the results of SFG-VS experiments.

Systematic review of brain arteriovenous malformation grading systems evaluating microsurgical treatment recommendation.

When evaluating brain arteriovenous malformations (bAVMs) for microsurgical resection, the natural history of bAVM rupture must be balanced against the perioperative risks. It is therefore adamant to have a reliable surgical grading system, balancing these important factors. This study systematically reviews the literature in order to identify and assess the quality of grading systems with regard to microsurgical bAVM treatment. A systematic literature review was performed to provide an overview of all available bAVM grading systems relevant for microsurgical treatment evaluation and to assess the most comprehensive grading system specifically for each subgroup of bAVM (i.e., unruptured, ruptured, and posterior fossa). Screening of 865 papers revealed thirteen grading systems for bAVM microsurgical risk stratification. Among them, two systems were specifically developed for ruptured bAVM and one specifically for posterior fossa bAVM. With one system being fundamentally different for supratentorial bAVM, the remaining nine systems used the same parameters: "size," "eloquence," "venous drainage," "arterial feeders," "age," "nidus compactness," and "hemorrhagic presentation". This study provides a comprehensive overview of all available bAVM grading systems relevant for surgical risk stratification. Furthermore, in the absence of a universal system appropriate to score all bAVMs, a workflow for selection of the best applicable scoring system in accordance with bAVM subgroups is presented.

Nanoliter-Scale Droplet-Droplet Microfluidic Microextraction Coupled with MALDI-TOF Mass Spectrometry for Metabolite Analysis of Cell Droplets.

The further miniaturization of liquid-phase microextraction (LPME) systems has important significance and major challenges for microscale sample analysis. Herein, we developed a rapid and flexible droplet-droplet microfluidic microextraction approach to perform nanoliter-scale miniaturized sample pretreatment, by combining droplet-based microfluidics, robotic liquid handling, and LPME techniques. Differing from the previous microextraction methods, both the extractant and sample volumes were decreased from the microliter scale or even milliliter scale to the nanoliter scale. We utilized the ability of a liquid-handling robot to manipulate nanoliter-scale droplets and micrometer-scale positioning to overcome the scaling effect difficulties in performing liquid-liquid extraction of nanoliter-volume samples in microsystems. Two microextraction modes, droplet-in-droplet microfluidic microextraction and droplet-on-droplet microfluidic microextraction, were developed according to the different solubility properties of the extractants. Various factors affecting the microextraction process were investigated, including the extraction time, recovery method of the extractant droplet, static and dynamic extraction mode, and cross-contamination. To demonstrate the validity and adaptability of the pretreatment and analysis of droplet samples with complex matrices, the present microextraction system coupled with MALDI-TOF mass spectrometry (MS) detection was applied to the quantitative determination of 7-ethyl-10-hydroxylcamptothecin (SN-38), an active metabolite of the anticancer drug irinotecan, in 800-nL droplets containing HepG2 cells. A linear relationship (y = 0.0305x + 0.376, R2 = 0.984) was obtained in the range of 4-100 ng/mL, with the limits of detection and quantitation being 2.2 and 4.5 ng/mL for SN-38, respectively.

Prediction of catalytic activities of bis(imino)pyridine metal complexes by machine learning.

This work demonstrates the potential of machine learning (ML) method to predict catalytic activity of transition metal complex precatalyst toward ethylene polymerization. For this purpose, 294 complexes and 15 molecular descriptors were selected to build the artificial neural network (ANN) model. The catalytic activity can be well predicted by the obtained ANN model, which was further validated by external complexes. Boruta algorithm was employed to explicitly decipher the importance of descriptors, illustrating the conjugated bond structure, and bulky substitutions are favorable for catalytic activity. The present work indicates that ML could give useful guidance for the new design of homogenous polyolefin catalyst.

6-Arylimino-2-(2-(1-phenylethyl)naphthalen-1-yl)-iminopyridylmetal (Fe and Co) Complexes as Highly Active Precatalysts for Ethylene Polymerization: Influence of Metal and/or Substituents on the Active, Thermostable Performance of Their Complexes and Resultant Polyethylenes.

A series of 6-arylimino-2-(2-(1-phenylethyl)naphthalen-1-yl)iminopyridines and their iron(II) and cobalt(II) complexes (Fe1-Fe5, Co1-Co5) were synthesized and routinely characterized as were Co3 and Co5 complexes, studied by single crystal X-ray crystallography, which individually displayed a distorted square pyramidal or trigonal bipyramid around a cobalt center. Upon treatment with either methyluminoxane (MAO) or modified methyluminoxane (MMAO), all complexes displayed high activities regarding ethylene polymerization even at an elevated temperature, enhancing the thermostability of the active species. In general, iron precatalysts showed higher activities than their cobalt analogs; for example, 10.9 × 106 g(PE) mol-1 (Co) h-1 by Co4 and 17.0 × 106 g(PE) mol-1 (Fe) h-1 by Fe4. Bulkier substituents are favored for increasing the molecular weights of the resultant polyethylenes, such as 25.6 kg mol-1 obtained by Co3 and 297 kg mol-1 obtained by Fe3. A narrow polydispersity of polyethylenes was observed by iron precatalysts activated by MMAO, indicating a single-site active species formed.

Unifying Molecular Weights of Highly Linear Polyethylene Waxes through Unsymmetrical 2,4-Bis(imino)pyridylchromium Chlorides.

By dealing CrCl3∙3THF with the corresponding ligands (L1-L5), an array of fluoro-substituted chromium (III) chlorides (Cr1-Cr5) bearing 2-[1-(2,4-dibenzhydryl-6-fluoro- phenylimino)ethyl]-6-[1-(arylimino)ethyl]pyridine (aryl = 2,6-Me2Ph Cr1, 2,6-Et2Ph Cr2, 2,6-iPr2Ph Cr3, 2,4,6-Me3Ph Cr4, 2,6-Et2-4-MePh Cr5) was synthesized in good yield and validated via Fourier Transform Infrared (FT-IR) spectroscopy and elemental analysis. Besides the routine characterizations, the single-crystal X-ray diffraction study revealed the solid-state structures of complexes Cr2 and Cr4 as the distorted-octahedral geometry around the chromium center. Activated by either methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), all the chromium catalysts exhibited high activities toward ethylene polymerization with the MMAO-promoted polymerizations far more productive than with MAO (20.14 × 106 g (PE) mol-1 (Cr) h-1 vs. 10.03 × 106 g (PE) mol-1 (Cr) h-1). In both cases, the resultant polyethylenes were found as highly linear polyethylene waxes with low molecular weights around 1-2 kg mol-1 and narrow molecular weight distribution (MWD range: 1.68-2.25). In general, both the catalytic performance of the ortho-fluorinated chromium complexes and polymer properties have been the subject of a detailed investigation and proved to be highly dependent on the polymerization reaction parameters (including cocatalyst type and amount, reaction temperature, ethylene pressure and run time).

Catalytic performance of bis(imino)pyridine Fe/Co complexes toward ethylene polymerization by 2D-/3D-QSPR modeling.

The two-dimensional and three-dimensional quantitative structure-property relationship (2D- and 3D-QSPR) approaches are applied to investigate the catalytic performance for a total data set of 55 bis(imino)pryridine iron and cobalt complexes, including the catalytic activity, molecular weight, and melting temperature of the product. The obtained models for the catalytic performance of interest exhibit good results by both 2D- and 3D-QSPR modeling, meanwhile higher predictive and validation powers observed in the 3D type. The modeling results indicate that the bulky substituents on ortho-position of the singular side phenyl ring and positive charge on para-position of the phenyl ring within the ligand are favorable to catalytic activity, while unfavorable to the molecular weight of product. Based on the obtained QSPR models, four new complexes are designed and predicted with good catalytic activity and very high molecular weight, which are in good agreement with our recent experimental report. © 2019 Wiley Periodicals, Inc.