Synthesis and structure of para‐toluene sulfonamide lanthanide complexes and their application in the polymerization of ε‐caprolactone

A series of para‐toluene sulfonamide ligands [TsNHPr‐i( HL ₁ ), TsNHBu‐t( HL ₂ ), TsNHPh( HL ₃ ), TsNHPhMe‐p( HL ₄ ), TsNHPhOMe‐p( HL ₅ )] were synthesized by amidation using para‐toluene sulfonyl chloride reacting with different primary amines. A series of homoleptic lanthanide complexes (Ln L₃, 1–10) (Ln = La, L = L₁ ( 1 ), Ln = Gd, L = L₂ ( 2 ), Ln = La, L = L₂ ( 3 ), Ln = Gd, L = L₂( 4 ), Ln = La, L = L₃ ( 5 ), Ln = Gd, L = L₃ ( 6 ), Ln = La, L = L₄ ( 7 ), Ln = Gd, L = L₄( 8 ), Ln = La, L = L₅ ( 9 ), Ln = Gd, L = L₅ ( 10 )) were prepared by amine elimination reactions of the ligands with Ln[N(SiMe₃)₂]₃ (Ln = La, Gd). Complexes 1 , 3 , 5 , 7 and 9 were all characterized by NMR spectra, and the structures of complex 3 was determined by single‐crystal X‐ray diffraction. Complex 3 crystallizes a binuclear cluster, consisting of two La³⁺ and six (TsNBu‐t)⁻ anions. Three (TsNBu‐t)⁻ anions are chelating to each La³⁺ as bidentate model with O and N forming three‐membered chelate rings; one of three anions is bridging to another La³⁺ via oxygen. All complexes were characterized using elemental analysis and infrared spectra. The catalytic properties of complexes 1–10 for the ring‐opening polymerization of ε‐caprolactone were studied and the results showed that all complexes are efficient initiators for this ring‐opening polymerization reaction.     

Measurement of rapid crack propagation in pressure pipes: A static S4 approach

A method for creating rapid crack propagation in pressurized pipes under slow static loading using modified S4 apparatus is described. In the development of the method a complexity involved with dynamic loading in the S4 test (ISO 13477) is eliminated by the use of a displacement controlled static loading machine. The experimental system consisted of an universal testing machine, a low compliance wedge loading device, notch tip quenching apparatus and a pipe specimen where a through thickness hole is drilled to accommodate the wedge loading device. The pipe specimen is made in such a way that a section containing a hole is free from the internal pressure, while the rest of the specimen is made to carry the internal pressure which would eventually drive the unstable crack along the pipe axis. The idea of such rapid crack initiation under static loading was derived from the concept of time-temperature equivalence, where impact loading may in part be simulated by lowering the temperature at the site of rapid crack initiation. The details of the method for rapid crack propagation under static loading are described and the correlation of the results to rapid crack propagation obtained by ISO 13477 is illustrated. The two methods were shown to compare quite well in terms of critical pressure determination and the details regarding normalized rapid crack length versus the internal pressure curve as well as the crack propagation pattern.     

Synthesis, characterization, and spectroscopic studies of palladium(II) and silver(I) complexes of 4-methoxybenzoylmethylenetriphenylphosphorane and 4-fluorobenzoylmethylenetriphenylphosphorane

The reactions of 4-methoxybenzoylmethylenetriphenylphosphorane ylide (MOBPPY), {(Ph)₃PCHCOC₆H₄OMe}, and 4-flourobenzoylmethylenetriphenylphosphorane ylide (FBPPY) with [Pd(C₆H₄CH₂NH₂-κ²-C-N)ClL] (L = Py, 3-MePy, 4-MePy, or PPh₃), in equimolar ratios in CH₂Cl₂ yield [Pd(C₆H₄CH₂NH₂-κ²-C-N)L (Ye)]TfO [(L = PPh₃, Ye = MOBPPY; L = PPh₃, Ye = FBPPY; L = Py, Ye = MOBPPY; or L = 3-MePy, Ye = MOBPPY]. The reaction of MOBPPY with AgOTf (OTf = CF₃SO₃) in molar ratios (2:1) using dry acetone as solvent gives [Ag(MOBPPY)₂]OTf.     

Direct fracture toughness determination of a ductile epoxy polymer from digital image correlation measurements on a single edge notched bending sample

This work presents a combined experimental and numerical study on the fracture toughness behaviour of a ductile epoxy resin system. Quasi-static fracture tests using single edge notched bending (SENB) specimens were conducted under room temperature conditions. In addition, the digital image correlation technique was employed to experimentally map the full-field displacements and strains around the notch and crack tip, allowing direct calculation of the J-integral fracture toughness. The magnitude of fracture toughness was found to be 1.52 ± 0.03 kJ/m², showing good consistency with the results measured according to the standard analytical formulations. A numerical model of the single edge notch bending specimen was built to compute the local strain field around the crack tip, together with the fracture toughness parameter. Good agreement was confirmed for both the experimental J-integral fracture toughness and the local surface strains around the crack-tip from the digital image correlation based optical technique, compared to the results obtained by numerical simulation. The fracture surfaces of the samples were examined using an optical microscope to analyze the failed surface morphology and the corresponding failure mechanisms.     

NMR,IR and DFT studies of phenylplatinum complexes with O-monodentate coordinated silsesquioxanate and auxiliary phosphine ligands

The molecular structure and spectroscopic properties of a series of phenylplatinum complexes containing silsesquioxanate and phosphine ligands with general formula trans-[Pt{O₁₀Si₇(R)₇(OH)₂}(Ph)(L)₂] (1: R = cyclo-C₅H₉, L = PEt₃; 2: R = iso-C₄H₉, L = PEt₃; 3: R = CH₃, L = PEt₃; 4: R = cyclo-C₅H₉, L = PMe₃; 5: R = cyclo-C₅H₉, L = PMe₂Ph; 6: R = cyclo-C₅H₉, L = PPh₂Me; 7: R = cyclo-C₅H₉, L = PPh₃) have been investigated by DFT/OPW91/6-31G(d) calculations, ¹H, ¹³C, ²⁹Si and ³¹P NMR and IR spectroscopy. DFT molecular modeling based on available X-ray and NMR data for complexes 1 and 2 allowed deriving structure-NMR spectra correlations. It was found that the alkyl substituents (R) attached to Si atoms, cyclo-C₅H₉, iso-C₄H₉ and CH₃, slightly influence the geometry and multinuclear NMR parameters of the complexes in the series studied. The molecular structures of the Pt(II) complexes with R = cyclo-C₅H₉ (4–7) were predicted by DFT calculations of their simplified models with R = CH₃ (4′?7′). The geometry optimizations of 4′?7′ showed square-planar configuration of Pt(II) center bonded to two trans phosphine ligands, a phenyl group and an O-monocoordinated silsesquioxanate. The structures 4′?6′ are stabilized by two intramolecular hydrogen bonds similar to 1 and 2. A fast conformer exchange process A?B and switching of H-bonds in solution of 1–6 were suggested based on (i) the calculated conformer energies and small barrier of the process, and (ii) the observed single ¹H NMR signal at low magnetic field. The stability of the Pt(II) complexes depends on the nature of the phosphine ligands and decreases in the order PMe₂Ph > PMe₃ > PPh₂Me > PEt₃ > PPh₃. The PPh₃ ligands attached to Pt(II) in 7 cause the largest geometry changes and a new set of weaker hydrogen bonds. The comparison of the calculated NMR and IR parameters with the experimental spectroscopic data reveals good coincidence and thus confirmed the suggested molecular structures.     

Dynamic crack growth characteristics of half-circular disk PMMA specimens with prefabricated penetration defects under impact loading

In this paper, the dynamic fracture experiment of half-circular disk PMMA specimens with prefabricated penetration defects under impact loading was carried out on the digital laser dynamic caustics experimental system (DLDC), the law of crack initiation, growth and traversing under different tilt angles (30°, 45°, 60°) was examined, and the variations of crack growth trajectory, velocity and DSIF at crack tip were compared for analysis. In addition, the discrete lattice spring method (DLSM) as a new development was employed to simulate how the dynamic cracks grew in PMMA specimens with defects, it was found that the numerical model can reproduce the experiment phenomenon. On the basis, the effect of the elastic modulus of the penetration defect medium on crack growth was analyzed. Referring to the experiment and numerical results, it was thus concluded that the angle and the elastic modulus of penetration defect would dramatically influence the crack growth characteristics.     

Chromium complexes based on thiophene–imine ligands for ethylene oligomerization

A new set of Cr(III) complexes, {L}CrCl₃(THF), based on thiophene–imine ( 2a , L = PhOC₆H₄(N═CH)‐2‐SC₄H₃; 2b , L = PhOC₂H₄(N═CH)‐2‐SC₄H₃; 2c , L = Ph(NH)C₂H₄(N═CH)‐2‐SC₄H₃; 2d , L = PhOC₆H₄(N═CH)‐2‐SC₄H₂‐5‐Ph; 2e , L = Ph(NH)C₂H₄(N═CH)‐2‐SC₄H₂‐5‐Ph) have been prepared and characterized using elemental analysis and infrared spectroscopy. Upon activation with methylaluminoxane, all the chromium complexes generated active systems affording a nonselective distribution of α‐olefins with turnover frequencies in the range 9500–93 500 (mol ethylene) (mol Cr)^?1 h^?1, and producing mostly oligomers (95.0–99.3 wt% of total products). Small amounts of polymer were produced in these oligomerization reactions (0.8–8.2 wt%). The catalytic activities were quite sensitive to the ligand environment. Moreover, the effects of oligomerization parameters (temperature, [Al]/[Cr] molar ratio, time) on the activity and on the product distribution were examined.     

High rate test method for fiber-matrix interface characterization

A new test method to directly characterize fiber-matrix interface properties under high rate of loading has been developed. A tensile Hopkinson bar with a modified incident bar is used to load a microdroplet test specimen. Numerical simulations were carried out to design the test specimen geometry and validate data reduction procedures for the dynamic interface experiments. Stress wave propagation in an S-2 Glass/Epoxy microdroplet specimen was studied with different droplet sizes (100 μm–200 μm) and fiber gage lengths (2 mm–6 mm). Simulation results indicate that dynamic equilibrium can be maintained up to a displacement rate of 10 m/s. Dynamic microdroplet experiments were conducted at a displacement rate of 1 m/s on S-2 glass/epoxy interface. Experimental results and post-failure inspection of the fiber matrix interface showed that the new test method is effective in measuring high rate interface properties of composites.     

A finite element method based comparative fracture assessment of carbon black and silica filled elastomers: Reinforcing efficacy of carbonaceous fillers in flexible composites

This study is focused on numerical investigation on fracture behaviors of carbon black (CB) and silica filled elastomeric composites. Finite element analysis (FEA) in compliance with multi-specimen method is used to calculate J-integral and geometry factor of the rubber composites up to a displacement of 20 mm for single edge notch in tension (SENT) and double edge notch in tension (DENT) specimens. An empirical relationship between crack tip opening displacement (CTOD) and crack advancement is established depending on notch to width ratio (NWR). The stress contours across the notches for SENT and DENT specimens is discussed briefly. It is found that fracture propagation resistance of CB filled elastomer is 125% more than that of silica filled elastomer. Although, Silica filled elastomer have good tensile strength and crosslink density but it fails to replace carbon black in terms of fracture properties. The critical J-integral for CB filled elastomer is 18.7% and 32.2% more than silica filled elastomer for SENT and DENT specimens respectively. The effect of specimen type on various fracture properties is also explored. The factor of safety is found to be significantly more in case of CB filled elastomers making them less vulnerable to crack propagation and catastrophic failure.     

‘A rendezvous with an old flame’: revisiting olefin hydrogenation with new rhodium and iridium catalysts

A novel tridentate hemilabile ligand 2 containing phosphine, imine and pyridyl donor groups has been prepared in analogy with the synthesis of the known related ligand 1. The reaction of 1 or 2 with 〚Rh(COE)₂Cl〛₂ resulted in the formation of the neutral complexes 〚Rh(L)Cl〛. By a method using 〚M(diene)Cl〛₂ as starting material, cationic complexes of the type 〚M(diene)(L)〛X were also obtained (M = Rh, diene = NBD, L = 1, 2; M = Ir, diene = COD, L = 1; X = BF₄, OTf). A comparative study of the catalytic activity of the new complexes towards the hydrogenation of various olefins has been reported. In particular, the catalysts of the type 〚Rh(L)Cl〛 are remarkably active when prepared in situ, especially for the reduction of hindered olefins.     

Synthesis, characterization of novel half-sandwich iridium and rhodium complexes containing pyridine-based organochalcogen ligands

A series of neutral pyridine-based organochalcogen ligands, 2,6-bis(1-methylimidazole-2-thione)pyridine (Bmtp), 2,6-bis(1-isopropylimidazole-2-thione)pyridine (Bptp), and 2,6-bis(1-tert-butylimidazole-2-thione)pyridine (Bbtp) have been synthesized and characterized. Reactions of [Cp*M(μ-Cl)Cl]₂ (Cp* = η⁵-pentamethylcyclopentadienyl, M = Ir, Rh) with three pyridine-based organochalcogen ligands result in the formation of the complexes Cp*M(L)Cl₂ (M = Ir, L = Bmtp, 1a·Cl₂; M = Rh, L = Bmtp, 1b·Cl₂; M = Ir, L = Bptp, 2a·Cl₂; M = Rh, L = Bptp, 2b·Cl₂; M = Ir, L = Bbtp, 3a·Cl₂; M = Rh, L = Bbtp, 3b·Cl₂), respectively. All compounds have been characterized by elemental analysis, NMR and IR spectra. The molecular structures of Bbtp, 1a·Cl₂, 1b·Cl₂, 2b·Cl₂ and 3b·Cl₂ have been determined by X-ray crystallography.     

Large area,waterproof, air stable and cost effective efficient perovskite solar cells through modified carbon hole extraction layer

The conventional unstable and expensive hole transporting materials (HTM) has been replaced by cost effective modified carbon hole extraction layer. Herein, we demonstrated a new recipe toward air stable and waterproof modified carbon hole extraction layer for efficient perovskite solar cells (PSCs). The commercial available carbon ink modified with methylammonium lead iodide (MAI) has been used as hole extraction layer for ambipolar perovskite solar cells. The fabricated optimized perovskite solar cell having Glass/FTO/mp-TiO₂/MAPbI_3-xCl_x/carbon + MAI/Carbon configuration exhibited η = 13.87% power conversion efficiency (PCE) with open circuit voltage (V_OC) 0.997 V, current density (J_SC) = 21.41 mAcm^?2 and fill factor (FF) 0.65. Furthermore, the air stability were tested at room temperature in open atmosphere. The water proof stability was tested under water flushing. Our results revealed that, although our carbon based devices show lower PCE (η = 13.87%) compared to spiro-MeOTAD HTM (η = 15%), the fabricated PSCs could even retain >90% after water exposure >20 times and ambient air stability more than 160 days. Further the large area device (>1 cm²) device shows 13.04% PCE with Jsc = 21.47 mAcm^?2, V_OC = 0.996 V and FF = 0.61. We have also demonstrated >13% efficiency for large area device (>1.1 cm²), demonstrating that the developed method is simple, cost effective and promising towards large area device fabrication. The developed methodology based on low cost carbon hole extraction layer will be helpful towards waterproof and air stable perovskite solar cells for large-area devices.     

Comparison of carbene and imidazole bonding to a copper(I) center

The bonding of (1,4,7-trithiacyclononane)copper(I) to N-methylimidazole and to N,N′-dimethylimidazol-2-ylidene (IMe) as its pseudo-tautomer has been compared by crystallography, spectroscopy, and electrochemical analyses. In the solid state, a shorter Cu-L bond is observed for L = carbene than for L = imidazole, which indicates that electronic effects override potential steric hindrance in this pair of complexes. The oxidation potential difference reveals that the imidazole is a substantially stronger donor than the carbene ligand, and it allowed for estimating the Lever electronic parameter for the carbene ligand, E_IMe = +0.30 V.     

Elemental analysis of airborne particulate matter collected on PTFE-membrane filters by SRXRF: A feasibility study

Summary Direct analysis of airborne particulate matter collected on PTFE-membrane filters was performed using synchrotron radiation X-ray fluorescence (SRXRF). Standard filter samples prepared in the laboratory were utilized to evaluate the setup performance as well as the capability of the proposed method. The influence of experimental parameters including the beam size and sample-to-detector distance were thoroughly examined. A total of 10 elements on the filter can be determined. It was found that the optimum detection efficiency for the system can be achieved if using a 3 mm′3 mm beam size as well as a 7 cm sample-to-detector distance with a two-step measurement procedure with photon energy less than 7 keV and 14 keV, respectively.     

Synthesis and characterization of 2-phenylaniline cyclopalladated complexes

Reaction of the dinuclear complex [Pd{κ2-N2′,C1-2-(2′-NH₂C₆H₄)C₆H₄}Cl]₂ (1) with ligands (L = 4-picoline, sym-collidine) gave the six-membered palladacycles [Pd{κ2-N2′,C1-2-(2′-NH₂C₆H₄)C₆H₄}Cl(L)] (2). The complex 1 reacted with AgX (X = CF₃SO₃, BF₄) and bidentate ligands [L–L = phen (phenanthroline), dppe (bis(diphenylphosphino)ethane), bipy(2,2′-bipyridine) and dppp (bis(diphenylphosphino)propane)] giving the mononuclear orthopalladated complexes [Pd{κ2-N2′,C1-2-(2′-NH₂C₆H₄)C₆H₄}(L–L)] (3) [L–L = phen, dppe, bipy and dppp]. These compounds were characterized by physico-chemical methods, and the structure of [Pd{κ2-N2′,C1-2-(2′-NH₂C₆H₄)C₆H₄}Cl(L)] (L = sym-collidine) was determined by single-crystal X-ray analysis.     

Vacancy diffusion in Cu Σ = 9 [110] twist grain boundary

Both the formation energy and the diffusive activation energy of a single vacancy migrating in the first four atomic layers intra- and inter-layer near Cu Σ = 9 [110] twist GB have been investigated by using the MAEAM. The formation of the vacancy is favorable on the first layer (1L) near the GB plane and is spontaneous on sites ‘2’–‘5’ especially ‘2’ and ‘4’. The effects of the GB on the intra- as well as inter-layer migration are mainly for 1L–1L as well as for 1L–1L′, 2L–1L and 3L–1L related to the 1L, respectively. Furthermore, the vacancy in 1L is favorable to migrate in 1L (intra-layer) or through GB plane to 1L′, the one in either 2L or 3L is favorable to migrate to 1L. So the vacancy tends to converge to the first layer near the GB plane.     

Response surface methodology for the optimization of the ultrasonic-assisted rhamnolipid treatment of oily sludge

This study investigates the recovery of oily sludge using ultrasound-assisted rhamnolipids and uses oil recovery yield as an evaluation index. The Box–Behnken response surface method was employed to investigate the individual and interactive effects of four different operating factors: frequency, dosage, liquid–solid ratio, and stirring speed. The model optimization results showed that the order of degree of influence of these four factors is frequency > liquid–solid ratio > dosage > stirring speed. The mathematical model predicted the highest oil recovery yield as 92.27%, which was highly accurate (in the 95% confidence interval) as from the experimental results, the highest oil recovery yield was 89.95% under optimal reaction conditions (frequency = 25.58 kHz, dosage = 150.45 mg/L, liquid–solid ratio = 4.1:1 mL/g, and stirring speed = 407 rpm). Thus, the deviation from the prediction model was only 2.32%, indicating that this method provides a theoretical basis for the treatment of oily sludge and can be implemented for practical application in Huaidong in the Xinjiang Province.     

X-ray analysis at 150?K, synthesis and theoretical calculations of 1-naphthaleneacrylic acid

The X-ray structure, synthesis, theoretical calculation and IR spectra of 1-naphthaleneacrylic acid are reported. The titled compound crystallizes in the monoclinic C 2/c space group with unit cell parameters: a = 14.556(3), b = 5.1332(10), c = 26.832(5) ?, β = 97.02(3)°, V = 1989.8(7) ?³, Z = 8 and form typical centrosymmetric hydrogen-bonded dimers. Theoretical calculations of 1-naphthylacrylic acid isolated molecule and hydrogen-bonded dimer have been carried out using density functional theory at the B3LYP level. For optimized structures the vibrational spectra have been then calculated and compared with experimental IR spectrum. The assignment and characterization of theoretical vibrational spectra were based on the potential energy distribution analysis. This comparison has shown that the theoretical spectrum for the dimer structure is in good agreement with the experimental one. Structural comparisons with naphthalene, and with some substituted 2-propenoic acids have shown influence of the substituent on conformation of the naphthalene ring or 2-propenoic moiety.     

Preparation of Bi0.4Sb1.6Se3xTe3(1−x) hexagonal rods and effect of Se on structure and electrical property

In the current study, novel hexagonal rods based on Bi_0.4Sb_1.6Te₃ raw materials and dispersed with x amounts of Se (x = 0.0, 0.2, 0.4, 0.6, 0.8, and 1.0) in the form Bi_0.4Sb_1.6Se_3xTe_3(1−x) were synthesized via a standard solid-state microwave route. The morphologies of these rods were explored using field emission scanning electron microscopy (FESEM). The crystalline of the powders were examined by X-ray diffraction (XRD), which showed that the powders of 0.0 ≤ x ≤ 0.8 samples can be indexed as the rhombohedral phase, whereas the sample with x = 1.0 has an orthorhombic phase structure. The influence of variations in Se content on thermoelectric properties was studied in the temperature range of 300–523 K. The alloying of Se in Bi_0.4Sb_1.6Te₃ effectively caused a decrease in hole concentration and, thus, a decrease in electrical conductivity and an increase in Seebeck coefficient. The maximal power factor measured in the present work was 7.47 mW/m K² at 373 K for the x = 0.8 sample.     

Detection of beryllium in digested autopsy tissues by inductively coupled plasma mass spectrometry using a high matrix interface configuration

This article describes a robust methodology using the combination of instrumental design (high matrix interface—HMI), sample dilution and internal standardization for the quantification of beryllium (Be) in various digested autopsy tissues using inductively coupled plasma mass spectrometry. The applicability of rhodium as a proper internal standard for Be was demonstrated in three types of biological matrices (i.e., femur, hair, lung tissues). Using HMI, it was possible to achieve instrumental detection limits and sensitivity of 0.6 ng L⁻¹ and 157 cps L ng⁻¹, respectively. Resilience to high salt matrices of the HMI setup was also highlighted using bone mimicking solution ([Ca²⁺] = 26 to 1,400 mg L⁻¹), providing a 14-fold increase in tolerance and a 2.7-fold decrease in method detection limit compared to optimized experimental conditions obtained without the HMI configuration. Precision of the methodology to detect low levels of Be in autopsy samples was demonstrated using hair and blood certified reference materials. Be concentration ranging from 0.015 to 255 μg kg⁻¹ in autopsy samples obtained from the U.S. Transuranium and Uranium Registries were measured using the methodology presented.