It is a well-known fact that sirolimus(SRL) undergoes degradation process via hydrolysis in aqueous media, leading to incorrect assessment of drug amount and thus release characteristics of formulations.The main objec...It is a well-known fact that sirolimus(SRL) undergoes degradation process via hydrolysis in aqueous media, leading to incorrect assessment of drug amount and thus release characteristics of formulations.The main objective of the present study was to evaluate the effect of nonionic surfactants in media on invitro release profiles for sirolimus eluting stents(SES) coated with biodegradable polymeric matrix.Phosphate buffer and acetate buffer incorporating nonionic surfactants with varying concentrations were examined for adequate solubility and stability(by RP-HPLC). Good sink condition was achieved in phosphate buffer(at pH 4.0) with 1.0% Tween 20, 1.0% Brij 35% and 0.5% Brij 58. Hydrodynamic size(by DLS) and the micelle-water partition coefficient(P) with standard free energy of solubilization(ΔGs°) of drug were evaluated to get some understanding about the solubilization phenomena. About 80% of drug release during the period of 48 h was achieved in optimized drug release media which was 1.0% Tween20 in phosphate buffer pH 4.0. The obtained accelerated SRL release profile in optimized medium correlated well with the real time in-vitro release in phosphate buffer(pH 7.4). Surface morphology changes(by SEM), changes in gravimetric weights and molecular weight change(by GPC) were examined before and after drug release to understand the drug release mechanism which explains that the polymer did not undergo degradation during the drug release.展开更多
Hollow calcium carbonate(CaCO3) microspheres with different morphologies were synthesized via the precipitation reaction of calcium chloride with sodium carbonate in the presence of different surfactant-polymer comp...Hollow calcium carbonate(CaCO3) microspheres with different morphologies were synthesized via the precipitation reaction of calcium chloride with sodium carbonate in the presence of different surfactant-polymer complexes.The selected anionic surfactants were sodium dodecyl sulfonate(SDS) and sodium dodecyl benzenesulfonate(SDBS),respectively.The selected water-soluble polymers were polyacrylic acid(PAA) and polyvinyl pyrrolidone(PVP).In this work,SDS-PVP "pearl-necklace model" micellar complex was formed via hydrophobic effectiveness between SDS and PVP and it served as the spherical template to generate spherical CaCO3 aggregates with hollow microspheres composed of about 500 nm irregular shaped particles.SDS-PAA complexes and SDBS-PAA complexes formed "core-shell model" aggregates with calcium ions serving as the medium to link the anionic surfactant and the polymer.SDS-PAA "core-shell model" aggregates would act as templates for hollow CaCO3 microspheres consisting of 30―50nm irregular shaped crystallites.SDBS-PAA "core-shell model" aggregates served as the spherical aggregate templates to generate spherical CaCO3 aggregates consisted of many small spherical particles which had grown together.All the obtained CaCO3 hollow microspheres are calcite particles.This research may provide new insight into the control of morphologies of hollow CaCO3 microspheres in the presence of surfactantpolymer complexes.展开更多
By means of changing the detection angle, the molecular conformation of a new type of polymer surfactant, acrylamide-poly(oxyethykene alkyl ether)acrylate-anionic monomer random copolymer, was studied by x-ray photoel...By means of changing the detection angle, the molecular conformation of a new type of polymer surfactant, acrylamide-poly(oxyethykene alkyl ether)acrylate-anionic monomer random copolymer, was studied by x-ray photoelectron spectroscopy(XPS) in detail.展开更多
Based on deep analysis of ASP/oil emulsions flow behavior characteristic,a mathematical description of non-Newtonian emulsion was developed,and variation of rheological behaviors along the percolation flow direction w...Based on deep analysis of ASP/oil emulsions flow behavior characteristic,a mathematical description of non-Newtonian emulsion was developed,and variation of rheological behaviors along the percolation flow direction was given.The effects of emulsions rheological behavior on oil recovery were quantity researched by a 2-D positive rhythm profile geological model.The result shows that the high viscosity and reduction of water phase permeability by emulsification can improve low-middle layer flow rate and enhance sweep efficiency,and the enhancement degree is related with emulsification degree.The study result can be used as reference for scheme design and production performance forecast during ASP flooding.展开更多
A surfactant-assisted method for preparing colloidal spheres with narrow size distribution from a polydispersed azo polymer has been developed in this work. The colloidal spheres were formed through gradual hydrophobi...A surfactant-assisted method for preparing colloidal spheres with narrow size distribution from a polydispersed azo polymer has been developed in this work. The colloidal spheres were formed through gradual hydrophobic aggregation of the polymeric chains in THF-H2O dispersion media, which was induced by a steady increase in the water content. Results showed that the addition of a small amount of surfactant (SDBS) could significantly narrow the size distribution of the colloidal spheres. The size distribution of the colloidal spheres was determined by the concentrations of azo polymer and the amount of surfactant in the systems. When the concentrations of polymer and surfactant amount were in a proper range, colloidal spheres with narrow size distribution could be obtained. The colloidal spheres formed by this method could be elongated along the polarization direction of the laser beams to be a new type of the colloid-based functional materials. upon Ar^+ laser irradiation. The colloidal spheres are considered展开更多
To understand the displacement characteristics and remaining oil displacement process by the surfactant/polymer(SP) flooding in cores with different pore structures, the effects of pore structure on the enhanced oil r...To understand the displacement characteristics and remaining oil displacement process by the surfactant/polymer(SP) flooding in cores with different pore structures, the effects of pore structure on the enhanced oil recovery of SP flooding was investigated at the pore, core and field scales through conducting experiments on natural core samples with three typical types of pore structures. First, the in-situ nuclear magnetic resonance core flooding test was carried out to capture the remaining oil variation features in the water flooding and SP flooding through these three types of cores. Subsequently, at the core scale, displacement characteristics and performances of water flooding and SP flooding in these three types of cores were evaluated based on the full-size core flooding tests. Finally, at the field scale, production characteristics of SP flooding in the bimodal sandstone reservoir and multimodal conglomerate reservoir were compared using the actual field production data. The results show: as the pore structure gets more and more complex, the water flooding performance gets poorer, but the incremental recovery factor by SP flooding gets higher;the SP flooding can enhance the producing degree of oil in 1-3 μm pores in the unimodal and bimodal core samples, while it produces largely oil in medium and large pores more than 3 μm in pore radius in the multimodal core sample. The core flooding test using full-size core sample demonstrates that the injection of SP solution can significantly raise up the displacement pressure of the multimodal core sample, and greatly enhance recovery factor by emulsifying the remaining oil and enlarging swept volume. Compared with the sandstone reservoir, the multimodal conglomerate reservoir is more prone to channeling. With proper profile control treatments to efficiently enlarge the microscopic and macroscopic swept volumes, SP flooding in the conglomerate reservoir can contribute to lower water cuts and longer effective durations.展开更多
Orthogonal-test-design method has been used to determine the optimal formula by phase behavior and interfacial tension studies, respectively. The effect of each component of two alkaline/surfactant/polymer flooding sy...Orthogonal-test-design method has been used to determine the optimal formula by phase behavior and interfacial tension studies, respectively. The effect of each component of two alkaline/surfactant/polymer flooding systems on interfacial tension is discussed, in which a low-price natural mixed carboxylate (SDC) is used as the major surfactant. The results indicate that the optimal composition is SDC (0.5%), alkaline NaHCO3/Na2CO3 with mass ratio of 1 (1.0%), and hydrolyzed polyacrylamide(0.1%). In the coreflood experiment, their oil recovery is increased by about 25.2% and 26.8% original oil in place, respectively.展开更多
The interfacial properties and rheological behavior of surfactant/polymer complex systems were measured to investigate the association behavior of the associating polymer.Compared with the pure surfactant solution,the...The interfacial properties and rheological behavior of surfactant/polymer complex systems were measured to investigate the association behavior of the associating polymer.Compared with the pure surfactant solution,there are two inflection points in the surface tension curve for the surfactant/polymer complex systems.The two inflection points are dependent on the surfactant type and polymer concentration.The effect of surfactant on the rheological behavior of polymer can be divided into two aspects.First,the addition of short-chain betaine surfactant is detrimental to the viscosity of polymer solution due to the electrostatic shielding effect.Second,long-chain betaine surfactant also reduces the viscosity of polymer solutions at low concentrations.However,when the concentration of the long-chain betaine surfactant is relatively high,the long-chain betaine surfactant could form worm-like micelles that promote the intermolecular association and thus increase the number of associating junctions,thereby resulting in the augmentation of viscosity.So it is necessary to apply the long-chain betaine surfactant to build the polymer/surfactant flooding system.The interaction model between surfactant and polymer is proposed,which is different from the traditional‘Three-Region Model’.展开更多
Nickel nanoparticles can work as catalyst for the aquathermolysis reactions between water and heavy oil.A homogeneous and stable suspension is needed to carry the nickel nanoparticles into deeper reservoirs.This study...Nickel nanoparticles can work as catalyst for the aquathermolysis reactions between water and heavy oil.A homogeneous and stable suspension is needed to carry the nickel nanoparticles into deeper reservoirs.This study conducts a detailed investigation on how to achieve stabilized nickel nanoparticle suspensions with the use of surfactant and polymer.To stabilize the nickel nanoparticle suspension,three surfactants including sodium dodecyl sulfate,cationic surfactant cetyltrimethylammonium bromide and polyoxyalkalene amine derivative(Hypermer) along with xanthan gum polymer were introduced into the nickel nanoparticle suspension.Static stability tests and zeta potential measurements were conducted to determine the polymer/surfactant recipes yielding the most stable nickel nanoparticle suspensions.Dynamic micromodel flow tests were also conducted on three suspensions to reveal how the nickel nanoparticles would travel and distribute in porous media.Test results showed that when the injection was initiated,most nickel nanoparticles were able to pass through the gaps between the sand grains and produced in the outlet of the micromodel;only a small number of the nickel nanoparticles were attached to the grain surface.A higher nickel concentration in the suspension may lead to agglomeration of nickel nanoparticles in porous media,while a lower concentration can mitigate this agglomeration.Moreover,clusters tended to form when the nickel nanoparticle suspension carried an electrical charge opposite to that of the porous media.Follow-up waterflood was initiated after the nanofluid injection.It was found that the waterflood could not flush away the nanoparticles that were remaining in the micromodel.展开更多
In this paper, the rigid structural thermosensitive polymer (made in lab) of NBS (N-butyl styrene), N, N-DEAM (diethyl acrylamide) and AM (acrylamide) was prepared. The influence of viscosity for copolymer sol...In this paper, the rigid structural thermosensitive polymer (made in lab) of NBS (N-butyl styrene), N, N-DEAM (diethyl acrylamide) and AM (acrylamide) was prepared. The influence of viscosity for copolymer solution under different reaction conditions such as temperatures and inorganic salt (monovalent salt and divalent salt) was analyzed. The experiment studies the combination of polymer situation and three different types of surfactants under certain conditions of the room temperature (25℃) and the formation temperature (76℃). At last, the influence of the surfactant kinds and concentration on the viscosity of the polymer solution are studied. The results show that: The copolymer solution, the apparent viscosity of which decreases with the increasement of temperature, but its viscosity has suddenly increased and thereafter dropped in the transition temperature. So the temperature sensitive effect ofcopolymer is very significantly. When the concentration of inorganic salt and surfactant can be controlled in certain extent, the copolymer solution, the effect increases with the increasement of the concentration, but the viscosity of which decreases with the increasement of shear rate. Shear rate can be controlled in certain extent, shearing stability properties of the copolymer solution are proved.展开更多
Dummy molecularly imprinted polymers (DMIPs) for 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) were produced using three structural analogues as dummy template molecules. The chosen analogues were 4-(a...Dummy molecularly imprinted polymers (DMIPs) for 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) were produced using three structural analogues as dummy template molecules. The chosen analogues were 4-(acetymethylamino)-1-(3-pyridyl)-butanol, 4- (methylamino)-1-(3-pyridyl)-1-butanol, and 1-(3-pyridyl)-1,4,-butanediol. The molecular recognition characteristics of the produced polymers were evaluated by X-ray photoelec- tron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR). Interactions between NNAL and methacrylic acid should be cooperative hydrogen bonds while the ni- trogen atom of the pyridine ring and the oxygen atom of the nitroso group in NNAL are two of the hydrogen-bond acceptors. It was further demonstrated that DMIP synthesized by 4-(acetymethylamino)-1-(3-pyridyl)-butanol had the best binding performance by XPS and FT-IR. Then dummy molecularly imprinted solid phase extraction (DMISPE) was developed for the determination of the analyte using the hit polymer as the sorbing material. Under optimal conditions, the recovery of NNAL dissolved in standard solution reached 93%. And the investigated polymer exhibited much higher binding of NNAL when nicotine was acted as the competitive molecule. Also the proposed method was applied to the measurement of NNAL spiked in blank urine samples with recoveries ranging from 87.2% to 101.2%.展开更多
Emulsifier-free poly(methyl methacrylate-styrene) [P(MMA-St)] nanospheres with an average particle size of 100 nm were synthesized in an isopropyl alcoholwater medium by a solvothermal method. Then, through radica...Emulsifier-free poly(methyl methacrylate-styrene) [P(MMA-St)] nanospheres with an average particle size of 100 nm were synthesized in an isopropyl alcoholwater medium by a solvothermal method. Then, through radical graft copolymerization of thermo-sensitive mono- mer N-isopropylacrylamide (NIPAm) and hydrophilic monomer acrylic acid (AA) onto the surface of P(MMA- St) nanospheres at 80 ℃, a series of thermo-sensitive polymer nanospheres, named SD-SEAL with different lower critical solution temperatures (LCST), were prepared by adjusting the mole ratio of NIPAm to AA. The products were characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, thermogravimetric analysis, particle size distribution, and specific surface area analysis. The temperature-sensitive behavior was studied by light transmittance tests, while the sealing performance was investigated by pressure transmission tests with Lungmachi Formation shales. The experimental results showed that the synthesized nanoparticles are sensitive to temperature and had apparent LCST values which increased with an increase in hydrophilic monomer AA. When the temperature was higher than its LCST value, SD- SEAL played a dual role of physical plugging and chemical inhibition, slowed down pressure transmission, and reduced shale permeability remarkably. The plugged layer of shale was changed to being hydrophobic, which greatly improved the shale stability展开更多
In this work, we synthesized a new Cd(Ⅱ) coordination polymer, [Cd(L)(cmb)H;O]· H;O(1), by using mixed 2-(carboxymethoxy)benzoic acid(H2 cmb) and typical chelating N-donor ligands 2-(2-fluoro-6-fluoro...In this work, we synthesized a new Cd(Ⅱ) coordination polymer, [Cd(L)(cmb)H;O]· H;O(1), by using mixed 2-(carboxymethoxy)benzoic acid(H2 cmb) and typical chelating N-donor ligands 2-(2-fluoro-6-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline ligand(L). 1 crystallizes in monoclinic, space group P21/c with a = 17.6150(8), b = 9.7811(4), c = 18.1603(8) ?, β = 118.9150(10)o, V = 2738.9(2) ?;, Z = 4, C28 H20 CdF2 N4 O7, Mr = 674.88, Dc = 1.637 g/cm3, F(000) = 1352, μ(Mo Ka) = 0.865 mm–1, R = 0.0643 and w R = 0.1976. In 1, the cmb2– anions link neighboring Cd(Ⅱ) atoms in a bis-chelating mode, yielding a one-dimensional chain structure along the b axis. The L ligands are attached on one side of the chain through chelating the Cd(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions to generate a one-dimensional double-chain structure. Furthermore, the one-dimensional double-chains are stacked by C–H???π interactions between the carbon atom of L ligand and the benzene ring of cmb2–ligand to give a layer structure. Moreover, the solid state luminescent property of 1 was also investigated at room temperature.展开更多
ABSTRACT Four novel 1D lanthanide coordination polymers with formula [Ln(3,4-pybz)3(HzO)2. H2O]n (Ln = 1 Sm; 2 Eu; 3 Tb; 4 Dy, 3,4-Hpybz = 3-(pyridin-4-yl)benzoic acid) have been synthesized by hydrothermal re...ABSTRACT Four novel 1D lanthanide coordination polymers with formula [Ln(3,4-pybz)3(HzO)2. H2O]n (Ln = 1 Sm; 2 Eu; 3 Tb; 4 Dy, 3,4-Hpybz = 3-(pyridin-4-yl)benzoic acid) have been synthesized by hydrothermal reactions of lanthanide oxide and 3-(pyridine-4-yl) benzoic acid. Single-crystal X-ray diffraction shows that the four compounds are isostructural. They all crystallize in a monoelinic system, space group P1^-. They have a doubly carboxylate-bridged infinite-chain structure with alternating Ln-(carboxylate)2-Ln linkages and one chelating carboxylate group on each metal center. The Ln ion also combines to two water molecules to form an eight-coordinate square antiprismatic geometry. The pyridine nitrogen atoms of the ligand do not coordinate to the metal centers but direct the formation of a 3D network through hydrogen bonding with coordinated water molecules. The photoluminescent properties of 2 and 3 have been also studied.展开更多
A new Cu(Ⅱ) coordination polymer, [Cu(L1)(L2)](1), was synthesized under hydrothermal conditions(H_2L1 = 4-(carboxymethoxy)benzoic acid, L2 = 2-(4-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline). Crystallograph...A new Cu(Ⅱ) coordination polymer, [Cu(L1)(L2)](1), was synthesized under hydrothermal conditions(H_2L1 = 4-(carboxymethoxy)benzoic acid, L2 = 2-(4-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline). Crystallographic data for 1: triclinic, space group P1 with a = 9.750(5), b = 10.148(5), c = 12.869(5) ?, α = 104.904(5), β = 102.133(5), γ = 95.219(5)°, V = 1188.7(10) ?~3, Z = 2, C_(28)H_(17)FN_4O_5Cu, Mr = 572.01, D_c = 1.598 g/cm^3, F(000) = 582, μ(MoKa) = 0.977 mm^(-1), R = 0.0474 and w R = 0.1144. The TGA behaviors and luminescence of 1 have been studied in detail. The L1 dianions link neighboring Cu(Ⅱ) atoms in a bis-chelating mode, yielding a one-dimensional chain structure along the b axis. The L2 ligands are attached on one side of the chain through chelating the Cu(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a layer structure. Additionally, the N–H???O hydrogen bonds further stabilize the structure of 1.展开更多
A new ID coordination polymer, [Cda(L1)2(L2)2].H2O (1, H2L1 = 4-(carboxy- methoxy)benzoic acid and L2 = 2-(4-fluorophenyl)-I H-imidazo[4,5-f][1,10]phenanthroline), has been hydrothermally synthesized and cha...A new ID coordination polymer, [Cda(L1)2(L2)2].H2O (1, H2L1 = 4-(carboxy- methoxy)benzoic acid and L2 = 2-(4-fluorophenyl)-I H-imidazo[4,5-f][1,10]phenanthroline), has been hydrothermally synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 9.985(5), b = 10.768(5), c = 12.512(5) A, a = 68.959(5), β = 80.354(5), γ = 79.663(5)°, V= 1227.4(10) A3, Z = 1, C56H36Cd2F2N8O11, Mr = 1259.73, Dc = 1.704 g/cm3, F(000) = 630, μ(MoKa) = 0.949 mm-1, R = 0.0261 and wR = 0.0655. The L1 anions link the neighboring Cd(II) atoms to form a 1D double chain structure. The L2 ligands are alternately located on both sides of the double chains. More interestingly, the lateral L2 ligands from adjacent double chains are paired to furnish strong π-π interactions, yielding a 2D supramolecular layer. N-H...O, O-H...N and O-H...O hydrogen bonds further stabilize the structure of 1. The luminescent property of 1 was studied in solid state at room temperature.展开更多
A new Cd(II) coordination polymer, namely, [Cd3(1,2,3-BTC)2(L)2]·2.25H2O (1, L = 2-(2-chloro-6-fluorophenyl)-1H-imidazo[4,5-A][1,10]phenanthroline and 1,2,3-BTC = 1,2,3-ben- zenetricarboxylate), has bee...A new Cd(II) coordination polymer, namely, [Cd3(1,2,3-BTC)2(L)2]·2.25H2O (1, L = 2-(2-chloro-6-fluorophenyl)-1H-imidazo[4,5-A][1,10]phenanthroline and 1,2,3-BTC = 1,2,3-ben- zenetricarboxylate), has been synthesized under hydrothermal conditions. The compound was characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group Pī with α = 11.650(2), b = 12.240(2), c = 19.760(4) A, α = 72.01(3), β = 77.11(3), γ = 83.48(3)°, V = 2609.4(9) A3, Z = 2, C56H31Cd3Cl2F2N8O14.25, Mr = 1489.99, Dc = 1.896 g/cm3, F(000) = 1466, μ(MoKa) = 1.401 mm^-1, R = 0.0401 and wR = 0.1104. Compound 1 shows a 1D chain structure, and the neigh- boring 1D chains of 1 are joined together by π···π interactions to result in a 2D supramolecular layer. In addition, the luminescent property of 1 has been studied in the solid state at room temperature.展开更多
A new Co(Ⅱ) coordination polymer, [Co(1,4-chdc)(L)(H2O)]n(1), was synthesized under hydrothermal condition(1,4-H2chdc = 1,4-cyclohexanedicarboxylic acid, L = 2-(4-fluoro-phenyl)-1 H-imidazo[4,5-f][1,10]p...A new Co(Ⅱ) coordination polymer, [Co(1,4-chdc)(L)(H2O)]n(1), was synthesized under hydrothermal condition(1,4-H2chdc = 1,4-cyclohexanedicarboxylic acid, L = 2-(4-fluoro-phenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline). Its crystal structure was determined by single-crystal X-ray diffraction. 1 crystallizes in triclinic, space group P1 with a = 8.790(5), b = 10.486(5), c = 13.305(5) ?, α = 87.391(5), β = 82.925(5), γ = 81.841(5)o, V = 1204.2(10) ?3, Z = 2, C27H23FN4O5Co, Mr = 561.42, Dc = 1.548 g/cm3, F(000) = 578, μ(Mo Ka) = 0.769 mm-1, R = 0.0415 and wR = 0.1043. In 1, each 1,4-chdc anion bridges two neighboring Co(Ⅱ) atoms to give a chain structure. The L ligands are attached on one side of the chain through chelating the Co(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a double-chain structure. The double-chain structures are linked into a supramolecular layer structure through N–H···O hydrogen-bonding interactions between the adjacent double-chain structures. Moreover, the thermal behavior of 1 was also studied.展开更多
Solvothermal reactions of 3,5-dimethyl-2,6-bis(3-(pyrid-2-yl)-1,2,4-triazolyl) pyridine (L), 1,4-benzendicarboxylic acid (H2bdc), and transitional metal cations of M11 (M = Mn, Co, Cd) in the presence of oxa...Solvothermal reactions of 3,5-dimethyl-2,6-bis(3-(pyrid-2-yl)-1,2,4-triazolyl) pyridine (L), 1,4-benzendicarboxylic acid (H2bdc), and transitional metal cations of M11 (M = Mn, Co, Cd) in the presence of oxalic acid (H2ox) afford three novel supramolecular polymers (CPs), namely, {[M2(ox)(L)2][bdc][M2(Hox)2(OH)(H2O)4]·3H2O}n (M = Mn for 1, Co for 2, Cd for 3). Single-crystal X-ray diffraction analysis reveals that complexes 1-3 are isostructural and the 3D supramolecular structure was connected through non-covalent interactions. With the help of H2ox, the L ligands cheated with center atoms forming a butterfly [M2(ox)(L)2]2+ building block. The bdc2- ligand linked with the unprecedented [M2(Hox)2(OH)2(H2O)4] units through strong O-H...O hydrogen bonds forming a zigzag chain, which are further connected through π-π interactions between L and bdc2- ligands to form a 3D supramolecular structure. Moreover, elemental analyses, IR, thermogravimetric, PXRD and luminescence have been investigated.展开更多
A novel Fe(II) coordination polymer [Fe(L)(trans-1,4-chdc)];~ has been hydrother- mally synthesized by using 1,4-cyclohexanedicarboxylic acid (1,4-H2chdc) and 2-(2-fluoro- phenyl)-lH-imidazo[4,5-f][1,10]phen...A novel Fe(II) coordination polymer [Fe(L)(trans-1,4-chdc)];~ has been hydrother- mally synthesized by using 1,4-cyclohexanedicarboxylic acid (1,4-H2chdc) and 2-(2-fluoro- phenyl)-lH-imidazo[4,5-f][1,10]phenanthroline (L). Crystallographic data: monoclinic, space group C2/c with a = 14.571(5), b = 32.389(6), c = 10.948(5)A, 18 = 115.186(5)°, V= 4676(3)A3, Z = 8, C27H21FFeN404, Mr = 540.33, De --- 1.535 g/cm3, F(000) = 2224, μ(MoKa) = 0.697 mmI, R = 0.0462 and wR = 0.1110. The two kinds of trans-l,4-chdc ligands link neighboring Fe(II) atoms to yield a two-dimensional layer structure. The π-π interactions between the L ligands of neighboring layers result in a three-dimensional supramolecular architecture. The IR and UV-vis spectra of the compound have been investigated in detail.展开更多
文摘It is a well-known fact that sirolimus(SRL) undergoes degradation process via hydrolysis in aqueous media, leading to incorrect assessment of drug amount and thus release characteristics of formulations.The main objective of the present study was to evaluate the effect of nonionic surfactants in media on invitro release profiles for sirolimus eluting stents(SES) coated with biodegradable polymeric matrix.Phosphate buffer and acetate buffer incorporating nonionic surfactants with varying concentrations were examined for adequate solubility and stability(by RP-HPLC). Good sink condition was achieved in phosphate buffer(at pH 4.0) with 1.0% Tween 20, 1.0% Brij 35% and 0.5% Brij 58. Hydrodynamic size(by DLS) and the micelle-water partition coefficient(P) with standard free energy of solubilization(ΔGs°) of drug were evaluated to get some understanding about the solubilization phenomena. About 80% of drug release during the period of 48 h was achieved in optimized drug release media which was 1.0% Tween20 in phosphate buffer pH 4.0. The obtained accelerated SRL release profile in optimized medium correlated well with the real time in-vitro release in phosphate buffer(pH 7.4). Surface morphology changes(by SEM), changes in gravimetric weights and molecular weight change(by GPC) were examined before and after drug release to understand the drug release mechanism which explains that the polymer did not undergo degradation during the drug release.
基金Supported by the National Natural Science Foundation of China(Nos.20771030,20671025)
文摘Hollow calcium carbonate(CaCO3) microspheres with different morphologies were synthesized via the precipitation reaction of calcium chloride with sodium carbonate in the presence of different surfactant-polymer complexes.The selected anionic surfactants were sodium dodecyl sulfonate(SDS) and sodium dodecyl benzenesulfonate(SDBS),respectively.The selected water-soluble polymers were polyacrylic acid(PAA) and polyvinyl pyrrolidone(PVP).In this work,SDS-PVP "pearl-necklace model" micellar complex was formed via hydrophobic effectiveness between SDS and PVP and it served as the spherical template to generate spherical CaCO3 aggregates with hollow microspheres composed of about 500 nm irregular shaped particles.SDS-PAA complexes and SDBS-PAA complexes formed "core-shell model" aggregates with calcium ions serving as the medium to link the anionic surfactant and the polymer.SDS-PAA "core-shell model" aggregates would act as templates for hollow CaCO3 microspheres consisting of 30―50nm irregular shaped crystallites.SDBS-PAA "core-shell model" aggregates served as the spherical aggregate templates to generate spherical CaCO3 aggregates consisted of many small spherical particles which had grown together.All the obtained CaCO3 hollow microspheres are calcite particles.This research may provide new insight into the control of morphologies of hollow CaCO3 microspheres in the presence of surfactantpolymer complexes.
文摘By means of changing the detection angle, the molecular conformation of a new type of polymer surfactant, acrylamide-poly(oxyethykene alkyl ether)acrylate-anionic monomer random copolymer, was studied by x-ray photoelectron spectroscopy(XPS) in detail.
基金Project(2005CB221300) supported by the Major State Basic Research Development Program of China
文摘Based on deep analysis of ASP/oil emulsions flow behavior characteristic,a mathematical description of non-Newtonian emulsion was developed,and variation of rheological behaviors along the percolation flow direction was given.The effects of emulsions rheological behavior on oil recovery were quantity researched by a 2-D positive rhythm profile geological model.The result shows that the high viscosity and reduction of water phase permeability by emulsification can improve low-middle layer flow rate and enhance sweep efficiency,and the enhancement degree is related with emulsification degree.The study result can be used as reference for scheme design and production performance forecast during ASP flooding.
基金The financial support by the NSFC under Projects (Nos. 50533040, 20374033) is gratefully acknowledged.
文摘A surfactant-assisted method for preparing colloidal spheres with narrow size distribution from a polydispersed azo polymer has been developed in this work. The colloidal spheres were formed through gradual hydrophobic aggregation of the polymeric chains in THF-H2O dispersion media, which was induced by a steady increase in the water content. Results showed that the addition of a small amount of surfactant (SDBS) could significantly narrow the size distribution of the colloidal spheres. The size distribution of the colloidal spheres was determined by the concentrations of azo polymer and the amount of surfactant in the systems. When the concentrations of polymer and surfactant amount were in a proper range, colloidal spheres with narrow size distribution could be obtained. The colloidal spheres formed by this method could be elongated along the polarization direction of the laser beams to be a new type of the colloid-based functional materials. upon Ar^+ laser irradiation. The colloidal spheres are considered
基金Supported by China National Science and Technology Major Project(2016ZX05025-003-010) and (2016ZX05010-005).
文摘To understand the displacement characteristics and remaining oil displacement process by the surfactant/polymer(SP) flooding in cores with different pore structures, the effects of pore structure on the enhanced oil recovery of SP flooding was investigated at the pore, core and field scales through conducting experiments on natural core samples with three typical types of pore structures. First, the in-situ nuclear magnetic resonance core flooding test was carried out to capture the remaining oil variation features in the water flooding and SP flooding through these three types of cores. Subsequently, at the core scale, displacement characteristics and performances of water flooding and SP flooding in these three types of cores were evaluated based on the full-size core flooding tests. Finally, at the field scale, production characteristics of SP flooding in the bimodal sandstone reservoir and multimodal conglomerate reservoir were compared using the actual field production data. The results show: as the pore structure gets more and more complex, the water flooding performance gets poorer, but the incremental recovery factor by SP flooding gets higher;the SP flooding can enhance the producing degree of oil in 1-3 μm pores in the unimodal and bimodal core samples, while it produces largely oil in medium and large pores more than 3 μm in pore radius in the multimodal core sample. The core flooding test using full-size core sample demonstrates that the injection of SP solution can significantly raise up the displacement pressure of the multimodal core sample, and greatly enhance recovery factor by emulsifying the remaining oil and enlarging swept volume. Compared with the sandstone reservoir, the multimodal conglomerate reservoir is more prone to channeling. With proper profile control treatments to efficiently enlarge the microscopic and macroscopic swept volumes, SP flooding in the conglomerate reservoir can contribute to lower water cuts and longer effective durations.
文摘Orthogonal-test-design method has been used to determine the optimal formula by phase behavior and interfacial tension studies, respectively. The effect of each component of two alkaline/surfactant/polymer flooding systems on interfacial tension is discussed, in which a low-price natural mixed carboxylate (SDC) is used as the major surfactant. The results indicate that the optimal composition is SDC (0.5%), alkaline NaHCO3/Na2CO3 with mass ratio of 1 (1.0%), and hydrolyzed polyacrylamide(0.1%). In the coreflood experiment, their oil recovery is increased by about 25.2% and 26.8% original oil in place, respectively.
基金Financial support by the Major Scientific and Technological Projects of CNPC under Grant(No.ZD 2019-183-007)。
文摘The interfacial properties and rheological behavior of surfactant/polymer complex systems were measured to investigate the association behavior of the associating polymer.Compared with the pure surfactant solution,there are two inflection points in the surface tension curve for the surfactant/polymer complex systems.The two inflection points are dependent on the surfactant type and polymer concentration.The effect of surfactant on the rheological behavior of polymer can be divided into two aspects.First,the addition of short-chain betaine surfactant is detrimental to the viscosity of polymer solution due to the electrostatic shielding effect.Second,long-chain betaine surfactant also reduces the viscosity of polymer solutions at low concentrations.However,when the concentration of the long-chain betaine surfactant is relatively high,the long-chain betaine surfactant could form worm-like micelles that promote the intermolecular association and thus increase the number of associating junctions,thereby resulting in the augmentation of viscosity.So it is necessary to apply the long-chain betaine surfactant to build the polymer/surfactant flooding system.The interaction model between surfactant and polymer is proposed,which is different from the traditional‘Three-Region Model’.
基金the financial support provided by NSERC Discovery Grants to T. Babadagli (No: RES0011227) and H. Li (No. NSERC RGPIN 05394)。
文摘Nickel nanoparticles can work as catalyst for the aquathermolysis reactions between water and heavy oil.A homogeneous and stable suspension is needed to carry the nickel nanoparticles into deeper reservoirs.This study conducts a detailed investigation on how to achieve stabilized nickel nanoparticle suspensions with the use of surfactant and polymer.To stabilize the nickel nanoparticle suspension,three surfactants including sodium dodecyl sulfate,cationic surfactant cetyltrimethylammonium bromide and polyoxyalkalene amine derivative(Hypermer) along with xanthan gum polymer were introduced into the nickel nanoparticle suspension.Static stability tests and zeta potential measurements were conducted to determine the polymer/surfactant recipes yielding the most stable nickel nanoparticle suspensions.Dynamic micromodel flow tests were also conducted on three suspensions to reveal how the nickel nanoparticles would travel and distribute in porous media.Test results showed that when the injection was initiated,most nickel nanoparticles were able to pass through the gaps between the sand grains and produced in the outlet of the micromodel;only a small number of the nickel nanoparticles were attached to the grain surface.A higher nickel concentration in the suspension may lead to agglomeration of nickel nanoparticles in porous media,while a lower concentration can mitigate this agglomeration.Moreover,clusters tended to form when the nickel nanoparticle suspension carried an electrical charge opposite to that of the porous media.Follow-up waterflood was initiated after the nanofluid injection.It was found that the waterflood could not flush away the nanoparticles that were remaining in the micromodel.
文摘In this paper, the rigid structural thermosensitive polymer (made in lab) of NBS (N-butyl styrene), N, N-DEAM (diethyl acrylamide) and AM (acrylamide) was prepared. The influence of viscosity for copolymer solution under different reaction conditions such as temperatures and inorganic salt (monovalent salt and divalent salt) was analyzed. The experiment studies the combination of polymer situation and three different types of surfactants under certain conditions of the room temperature (25℃) and the formation temperature (76℃). At last, the influence of the surfactant kinds and concentration on the viscosity of the polymer solution are studied. The results show that: The copolymer solution, the apparent viscosity of which decreases with the increasement of temperature, but its viscosity has suddenly increased and thereafter dropped in the transition temperature. So the temperature sensitive effect ofcopolymer is very significantly. When the concentration of inorganic salt and surfactant can be controlled in certain extent, the copolymer solution, the effect increases with the increasement of the concentration, but the viscosity of which decreases with the increasement of shear rate. Shear rate can be controlled in certain extent, shearing stability properties of the copolymer solution are proved.
文摘Dummy molecularly imprinted polymers (DMIPs) for 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) were produced using three structural analogues as dummy template molecules. The chosen analogues were 4-(acetymethylamino)-1-(3-pyridyl)-butanol, 4- (methylamino)-1-(3-pyridyl)-1-butanol, and 1-(3-pyridyl)-1,4,-butanediol. The molecular recognition characteristics of the produced polymers were evaluated by X-ray photoelec- tron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR). Interactions between NNAL and methacrylic acid should be cooperative hydrogen bonds while the ni- trogen atom of the pyridine ring and the oxygen atom of the nitroso group in NNAL are two of the hydrogen-bond acceptors. It was further demonstrated that DMIP synthesized by 4-(acetymethylamino)-1-(3-pyridyl)-butanol had the best binding performance by XPS and FT-IR. Then dummy molecularly imprinted solid phase extraction (DMISPE) was developed for the determination of the analyte using the hit polymer as the sorbing material. Under optimal conditions, the recovery of NNAL dissolved in standard solution reached 93%. And the investigated polymer exhibited much higher binding of NNAL when nicotine was acted as the competitive molecule. Also the proposed method was applied to the measurement of NNAL spiked in blank urine samples with recoveries ranging from 87.2% to 101.2%.
基金financial support from the National Science Foundation of China (Nos. 51374233, 51474235)the Postdoctoral Innovative Project Foundation of Shandong Province (No. 201602027)+2 种基金the Qingdao Postdoctoral Applied Research Project (No. 2015242)the Fundamental Research Funds for the Central Universities (No. 15CX06021A)the Graduate Student Innovation Project from China University of Petroleum (East China) (No. YCX2015011)
文摘Emulsifier-free poly(methyl methacrylate-styrene) [P(MMA-St)] nanospheres with an average particle size of 100 nm were synthesized in an isopropyl alcoholwater medium by a solvothermal method. Then, through radical graft copolymerization of thermo-sensitive mono- mer N-isopropylacrylamide (NIPAm) and hydrophilic monomer acrylic acid (AA) onto the surface of P(MMA- St) nanospheres at 80 ℃, a series of thermo-sensitive polymer nanospheres, named SD-SEAL with different lower critical solution temperatures (LCST), were prepared by adjusting the mole ratio of NIPAm to AA. The products were characterized by Fourier transform infrared spectroscopy, transmission electron microscopy, thermogravimetric analysis, particle size distribution, and specific surface area analysis. The temperature-sensitive behavior was studied by light transmittance tests, while the sealing performance was investigated by pressure transmission tests with Lungmachi Formation shales. The experimental results showed that the synthesized nanoparticles are sensitive to temperature and had apparent LCST values which increased with an increase in hydrophilic monomer AA. When the temperature was higher than its LCST value, SD- SEAL played a dual role of physical plugging and chemical inhibition, slowed down pressure transmission, and reduced shale permeability remarkably. The plugged layer of shale was changed to being hydrophobic, which greatly improved the shale stability
基金Supported by the National Natural Science Foundation of China(No.21607051)Institute Foundation of Siping City(No.2017057)the Science and Technology Research Projects of the Education Committee of Jilin Province(No.JJKH20180779KJ)
文摘In this work, we synthesized a new Cd(Ⅱ) coordination polymer, [Cd(L)(cmb)H;O]· H;O(1), by using mixed 2-(carboxymethoxy)benzoic acid(H2 cmb) and typical chelating N-donor ligands 2-(2-fluoro-6-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline ligand(L). 1 crystallizes in monoclinic, space group P21/c with a = 17.6150(8), b = 9.7811(4), c = 18.1603(8) ?, β = 118.9150(10)o, V = 2738.9(2) ?;, Z = 4, C28 H20 CdF2 N4 O7, Mr = 674.88, Dc = 1.637 g/cm3, F(000) = 1352, μ(Mo Ka) = 0.865 mm–1, R = 0.0643 and w R = 0.1976. In 1, the cmb2– anions link neighboring Cd(Ⅱ) atoms in a bis-chelating mode, yielding a one-dimensional chain structure along the b axis. The L ligands are attached on one side of the chain through chelating the Cd(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions to generate a one-dimensional double-chain structure. Furthermore, the one-dimensional double-chains are stacked by C–H???π interactions between the carbon atom of L ligand and the benzene ring of cmb2–ligand to give a layer structure. Moreover, the solid state luminescent property of 1 was also investigated at room temperature.
基金Supported by NSFC 20973174 and MOST project (2006DFA43020 and 2007CB815307)
文摘ABSTRACT Four novel 1D lanthanide coordination polymers with formula [Ln(3,4-pybz)3(HzO)2. H2O]n (Ln = 1 Sm; 2 Eu; 3 Tb; 4 Dy, 3,4-Hpybz = 3-(pyridin-4-yl)benzoic acid) have been synthesized by hydrothermal reactions of lanthanide oxide and 3-(pyridine-4-yl) benzoic acid. Single-crystal X-ray diffraction shows that the four compounds are isostructural. They all crystallize in a monoelinic system, space group P1^-. They have a doubly carboxylate-bridged infinite-chain structure with alternating Ln-(carboxylate)2-Ln linkages and one chelating carboxylate group on each metal center. The Ln ion also combines to two water molecules to form an eight-coordinate square antiprismatic geometry. The pyridine nitrogen atoms of the ligand do not coordinate to the metal centers but direct the formation of a 3D network through hydrogen bonding with coordinated water molecules. The photoluminescent properties of 2 and 3 have been also studied.
基金Supported by the National Natural Science Foundation of China(No.21607051)Institute Foundation of Siping City(No.2017057)the Science and Technology Research Projects of the Education Committee of Jilin Province(No.JJKH20180779KJ)
文摘A new Cu(Ⅱ) coordination polymer, [Cu(L1)(L2)](1), was synthesized under hydrothermal conditions(H_2L1 = 4-(carboxymethoxy)benzoic acid, L2 = 2-(4-fluorophenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline). Crystallographic data for 1: triclinic, space group P1 with a = 9.750(5), b = 10.148(5), c = 12.869(5) ?, α = 104.904(5), β = 102.133(5), γ = 95.219(5)°, V = 1188.7(10) ?~3, Z = 2, C_(28)H_(17)FN_4O_5Cu, Mr = 572.01, D_c = 1.598 g/cm^3, F(000) = 582, μ(MoKa) = 0.977 mm^(-1), R = 0.0474 and w R = 0.1144. The TGA behaviors and luminescence of 1 have been studied in detail. The L1 dianions link neighboring Cu(Ⅱ) atoms in a bis-chelating mode, yielding a one-dimensional chain structure along the b axis. The L2 ligands are attached on one side of the chain through chelating the Cu(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a layer structure. Additionally, the N–H???O hydrogen bonds further stabilize the structure of 1.
基金Supported by Jilin Province Science and Technology Development projects (No. 201105085)
文摘A new ID coordination polymer, [Cda(L1)2(L2)2].H2O (1, H2L1 = 4-(carboxy- methoxy)benzoic acid and L2 = 2-(4-fluorophenyl)-I H-imidazo[4,5-f][1,10]phenanthroline), has been hydrothermally synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 9.985(5), b = 10.768(5), c = 12.512(5) A, a = 68.959(5), β = 80.354(5), γ = 79.663(5)°, V= 1227.4(10) A3, Z = 1, C56H36Cd2F2N8O11, Mr = 1259.73, Dc = 1.704 g/cm3, F(000) = 630, μ(MoKa) = 0.949 mm-1, R = 0.0261 and wR = 0.0655. The L1 anions link the neighboring Cd(II) atoms to form a 1D double chain structure. The L2 ligands are alternately located on both sides of the double chains. More interestingly, the lateral L2 ligands from adjacent double chains are paired to furnish strong π-π interactions, yielding a 2D supramolecular layer. N-H...O, O-H...N and O-H...O hydrogen bonds further stabilize the structure of 1. The luminescent property of 1 was studied in solid state at room temperature.
基金Supported by the Science and Technology Research Projects of the Education Committee of Jilin Province(No.2013212)
文摘A new Cd(II) coordination polymer, namely, [Cd3(1,2,3-BTC)2(L)2]·2.25H2O (1, L = 2-(2-chloro-6-fluorophenyl)-1H-imidazo[4,5-A][1,10]phenanthroline and 1,2,3-BTC = 1,2,3-ben- zenetricarboxylate), has been synthesized under hydrothermal conditions. The compound was characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group Pī with α = 11.650(2), b = 12.240(2), c = 19.760(4) A, α = 72.01(3), β = 77.11(3), γ = 83.48(3)°, V = 2609.4(9) A3, Z = 2, C56H31Cd3Cl2F2N8O14.25, Mr = 1489.99, Dc = 1.896 g/cm3, F(000) = 1466, μ(MoKa) = 1.401 mm^-1, R = 0.0401 and wR = 0.1104. Compound 1 shows a 1D chain structure, and the neigh- boring 1D chains of 1 are joined together by π···π interactions to result in a 2D supramolecular layer. In addition, the luminescent property of 1 has been studied in the solid state at room temperature.
基金Supported by the National Natural Science Foundation of China(No.21607051)
文摘A new Co(Ⅱ) coordination polymer, [Co(1,4-chdc)(L)(H2O)]n(1), was synthesized under hydrothermal condition(1,4-H2chdc = 1,4-cyclohexanedicarboxylic acid, L = 2-(4-fluoro-phenyl)-1 H-imidazo[4,5-f][1,10]phenanthroline). Its crystal structure was determined by single-crystal X-ray diffraction. 1 crystallizes in triclinic, space group P1 with a = 8.790(5), b = 10.486(5), c = 13.305(5) ?, α = 87.391(5), β = 82.925(5), γ = 81.841(5)o, V = 1204.2(10) ?3, Z = 2, C27H23FN4O5Co, Mr = 561.42, Dc = 1.548 g/cm3, F(000) = 578, μ(Mo Ka) = 0.769 mm-1, R = 0.0415 and wR = 0.1043. In 1, each 1,4-chdc anion bridges two neighboring Co(Ⅱ) atoms to give a chain structure. The L ligands are attached on one side of the chain through chelating the Co(Ⅱ) atoms, and are stacked with those of an adjacent chain through π-π interactions, yielding a double-chain structure. The double-chain structures are linked into a supramolecular layer structure through N–H···O hydrogen-bonding interactions between the adjacent double-chain structures. Moreover, the thermal behavior of 1 was also studied.
基金supported by the National Natural Science Foundation of China (No. 21101097)Natural Science Foundation of Shandong Province (ZR2010BQ023)the State Key Laboratory of Solid Lubrication (No. 0701)
文摘Solvothermal reactions of 3,5-dimethyl-2,6-bis(3-(pyrid-2-yl)-1,2,4-triazolyl) pyridine (L), 1,4-benzendicarboxylic acid (H2bdc), and transitional metal cations of M11 (M = Mn, Co, Cd) in the presence of oxalic acid (H2ox) afford three novel supramolecular polymers (CPs), namely, {[M2(ox)(L)2][bdc][M2(Hox)2(OH)(H2O)4]·3H2O}n (M = Mn for 1, Co for 2, Cd for 3). Single-crystal X-ray diffraction analysis reveals that complexes 1-3 are isostructural and the 3D supramolecular structure was connected through non-covalent interactions. With the help of H2ox, the L ligands cheated with center atoms forming a butterfly [M2(ox)(L)2]2+ building block. The bdc2- ligand linked with the unprecedented [M2(Hox)2(OH)2(H2O)4] units through strong O-H...O hydrogen bonds forming a zigzag chain, which are further connected through π-π interactions between L and bdc2- ligands to form a 3D supramolecular structure. Moreover, elemental analyses, IR, thermogravimetric, PXRD and luminescence have been investigated.
基金Supported by the Institute Foundation of Siping City(No.2009011)
文摘A novel Fe(II) coordination polymer [Fe(L)(trans-1,4-chdc)];~ has been hydrother- mally synthesized by using 1,4-cyclohexanedicarboxylic acid (1,4-H2chdc) and 2-(2-fluoro- phenyl)-lH-imidazo[4,5-f][1,10]phenanthroline (L). Crystallographic data: monoclinic, space group C2/c with a = 14.571(5), b = 32.389(6), c = 10.948(5)A, 18 = 115.186(5)°, V= 4676(3)A3, Z = 8, C27H21FFeN404, Mr = 540.33, De --- 1.535 g/cm3, F(000) = 2224, μ(MoKa) = 0.697 mmI, R = 0.0462 and wR = 0.1110. The two kinds of trans-l,4-chdc ligands link neighboring Fe(II) atoms to yield a two-dimensional layer structure. The π-π interactions between the L ligands of neighboring layers result in a three-dimensional supramolecular architecture. The IR and UV-vis spectra of the compound have been investigated in detail.