Solvothermal reactions of 4,4＇-oxybis（benzoic acid） （H2oba） with 1,3-dipyridyl benzene （1,3-dpb） produced a two-dimensional （2D） cadmium（Ⅱ） coordination polymer {[Cd（oba）（dpb）]·H2O}n （1）. The co...Solvothermal reactions of 4,4＇-oxybis（benzoic acid） （H2oba） with 1,3-dipyridyl benzene （1,3-dpb） produced a two-dimensional （2D） cadmium（Ⅱ） coordination polymer {[Cd（oba）（dpb）]·H2O}n （1）. The complex was characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group C2/c with a = 13.6692（9）, b = 25.9647（17）, c = 8.7912（6） , α = 125.0370（10）, γ = 2544.7（3）°, V = 2544.7（3） 3, C30H22N2O6Cd, Mr = 618.91, Dc =1.609 g/cm3, F（000） = 1248, μ = 0.904 mm-1 and Z = 4. The neighboring Cd（Ⅱ） ions are linked by oba2-anions and 1,3-dpb to form an infinitely 2D wavelike sheet, and two such 2D sheets are interlocked with each other by H-bonding to form a 2D → 2D structure. The adjacent two groups of interlocked structures are further linked to form a bilayer 2D supramolecular network by π-π interactions. In addition, the fluorescence property of 1 was also studied.展开更多
A novel soluble regular ladder poly（benzoyl-3-aminopropyl） silsesquioxane （LPBAS） was facilely prepared under effective assistance of concerted H-bonding self-assembly of amido groups of side chains and silanol gr...A novel soluble regular ladder poly（benzoyl-3-aminopropyl） silsesquioxane （LPBAS） was facilely prepared under effective assistance of concerted H-bonding self-assembly of amido groups of side chains and silanol groups, respectively, of a new template monomer [1,3-bis（benzoyl-3-aminopropyl）-1,1,3,3-tetraethoxydisiloxane] （M）. The ordered ladder structure of LPBAS is manifested in： （1） the presence of two Bragg peaks representing the ladder width （d） and ladder thickness （t） in X-ray diffraction （XRD） pattern; （2） narrow base-line width （w = 6） of resonance absorption for -CH2SiO3/2 moiety in 29Si-NMR and （3） high glass transition temperature Tg = 1 12℃ in differential scanning calorimetry （DSC） analysis.展开更多
The aim of this study was to develop an intravenous clarithromycin lipid emulsion(CLE)with good stability and excellent antibacterial activity. The CLE was prepared by the thinfilm dispersed homogenization method. The...The aim of this study was to develop an intravenous clarithromycin lipid emulsion(CLE)with good stability and excellent antibacterial activity. The CLE was prepared by the thinfilm dispersed homogenization method. The interaction between clarithromycin(CLA) and cholesteryl hemisuccinate(CHEMS) was confirmed by DSC, FT-IR and^1H NMR analysis. The interfacial drug loading, thermal sterilization, freeze–thaw stability, and in vitro and in vivo antibacterial activity were investigated systematically. DSC, FT-IR and^1H NMR spectra showed that CHEMS(CLA: CHEMS, M ratio 1:2) could interact with CLA through H-bonding and a hydrogen-bonded ion pair. The CHEMS was found necessary to maintain the stability of CLE.Ultracentrifugation showed that almost 88% CLA could be loaded into the interfacial layer.The optimized CLE formulation could withstand autoclaving at 121 °C for 10 min and remain stable after three freeze–thaw cycles. The in vitro susceptibility test revealed that the CLA–CHEMS ion-pair and CLE have similar activity to the parent drug against many different bacterial strains. The in vivo antibacterial activity showed that the ED50 of intravenous CLE was markedly lower than that of CLA solution administrated orally. CLE exhibited pronounced antibacterial activity and might be a candidate for a new nanocarrier for CLA with potential advantages over the current commercial formulation.展开更多
A highly ordered m-phenylenediimino-bridged ladder polyhydrosiloxane （abbr. OLPHS） with Mn = 1.24 × 10^4 was synthesized stoichiometric hydrolysis and dehydrochlorination condensation reaction between Si-Cl and...A highly ordered m-phenylenediimino-bridged ladder polyhydrosiloxane （abbr. OLPHS） with Mn = 1.24 × 10^4 was synthesized stoichiometric hydrolysis and dehydrochlorination condensation reaction between Si-Cl and Si-OH bonds. The complete ladder structure of OLPHS has been confirmed by the following three data. Two characteristic Bragg＇s peaks representing the ladder width （w = 0.94 nm） and ladder thickness （t = 0.42 nm） were observed in XRD analysis, which are consistent with those calculated by molecular simulation. The very sharp absorption with a small half-peak width （w1/2 = 0.5 ppm） for [（-HN）HSiO2/2]n moiety of OLPHS in ^29Si NMR spectrum indicated presence of the complete ladder structure. As collateral evidence, a higher glass transition temperature （Tg = 105 ℃） is also recorded in the DSC measurement, implying the high stiffness of ladder chain of OLPHS.展开更多
A novel soluble and reactive amide-bridged ladderlike polyhydrosiloxane （ALPHS） was first synthesized by an amido H-bonding self-assembled template. ALPHS with molecular weight M^-a = 18300 has very highly ordered l...A novel soluble and reactive amide-bridged ladderlike polyhydrosiloxane （ALPHS） was first synthesized by an amido H-bonding self-assembled template. ALPHS with molecular weight M^-a = 18300 has very highly ordered ladderlike structure, which was confirmed by a sharp resonance absorption peak of [-Si（H）O2/2 ] moiety with the half peak width △1/2 〈 0.5 in^29Si-NMR spectrum. Presence of the reactive Si-H groups gives ALPHS an opportunity to further derive a variety of functional polymers by versatile Si-H reactions such as hydrosilylation, condensation, and so on.展开更多
A novel, reactive amide-bridged ladder polyvinylsiloxane （abbr. LP） with Mn= 2.4×10^4 was synthesized for the first time by means of aryl amide H-bonding self-assembled template. The regularity of LP was charac...A novel, reactive amide-bridged ladder polyvinylsiloxane （abbr. LP） with Mn= 2.4×10^4 was synthesized for the first time by means of aryl amide H-bonding self-assembled template. The regularity of LP was characterized by the XRD, ^29Si NMR and DSC methods. XRD analysis demonstrated the ladder width w = 9.09A and the ladder thickness t = 3.89A, respectively, which are approximately consistent with the molecular simulation-calculated ones： w＇= 10.60A and t＇= 3.06A. ^29Si NMR displayed a resonance peak with small half peak width, △1/2 - 4 ppm, for the moiety [=Si（Vi）O2/2-]n of LP. Besides, as a collateral evidence, DSC measurement revealed a high glass transition temperature Tg = 225℃, suggesting high stiffness of the ladder main chain of LP.展开更多
Design and preparation of highly efficient zeolite catalysts for gas-phase Beckmann rearrangement of cyclohexanone oxime to caprolactam are attractive but still challenging.Herein,we show a one-pot synthesis of silica...Design and preparation of highly efficient zeolite catalysts for gas-phase Beckmann rearrangement of cyclohexanone oxime to caprolactam are attractive but still challenging.Herein,we show a one-pot synthesis of silicalite-1 zeolite nanosheets with rich H-bonded silanols.The key to this success is the use of urea in the synthetic system.Catalytic tests of cyclohexanone oxime gas-phase Beckmann rearrangement show that the silicalite-1 zeolite nanosheets with H-bonded silanols exhibit higher selectivity for caprolactam and longer reaction lifetime than those of the conventional silicalite-1 zeolite.Theoretical simulations reveal that the ammonium decomposed by urea is a critical additive for the formation of H-bond silanols.Obviously,one-pot synthesis of silicalite-1 zeolite nanosheets with rich H-bonded silanols plus excellent catalytic performance in the Beckmann rearrangement offer a new opportunity for development of highly efficient zeolites for catalytic applications in the future.展开更多
The title compound (C17H16O2, Mr = 252.30) crystallizes in the monoclinic system, space group P21/c with a = 11.5763(14), b = 11.0321(11), c = 11.5094(13) ?, β = 114.581(3)o, V = 1336.7(3) ?3 , Z = 4, Dc = 1.254 g/...The title compound (C17H16O2, Mr = 252.30) crystallizes in the monoclinic system, space group P21/c with a = 11.5763(14), b = 11.0321(11), c = 11.5094(13) ?, β = 114.581(3)o, V = 1336.7(3) ?3 , Z = 4, Dc = 1.254 g/cm3, μ(MoKa) = 0.081 cm-1 and F(000) = 536.00. The final R and wR are 0.0527 and 0.1285, respectively for 3058 observed reflections (I > 2σ(I)). In the title molecule, two phenyl rings are rotated oppositely with respect to the central part C(1)–C(2)=C(3)– C(4) (plane 3) and the dihedral angle between them is 14.8o. The phenone O(1) atom deviates from plane 3 by 0.291 ?. In the crystal the molecules form H-bond chains of R2 (6) and R2 (5) types 1 1 along [001]. The molecule chains interacted through three cooperative C–H…O H-bonds (R3 (11)) 1 in the ‘bay area’ (Fig. 3), extending along [010] and forming layer (100). Between the layers, there exist C–H/π interactions along [101]. Studies on the cooperative C–H…O H-bonds R3 (11) in the 1 similar crystals are also presented.展开更多
Organocatalytic ring-opening polymerization(ROP)is a more sustainable approach for synthesizing renewable and biodegradable polymers compared to conventional metal-based catalysis.A key challenge in the field has been...Organocatalytic ring-opening polymerization(ROP)is a more sustainable approach for synthesizing renewable and biodegradable polymers compared to conventional metal-based catalysis.A key challenge in the field has been applying organocatalysis under the harsh conditions of industrial ROP while maintaining high activity and selectivity.Herein,we present an efficient N-heterocyclic carbene/thiourea binary organocatalyst system(NHC/TU-2)for the ROP of lactide(LA)at elevated temperatures,offering excellent control by almost completely suppressing transesterification and epimerization.It was found that NHC/TU-2 operates according to the imidate H-bonding catalysis model;however,its notable feature is that the strength of the H-bonding is regulated by temperature,enabling the activation of the monomers with high selectivity.Additionally,the large size of the NHC/TU-2 complex introduces steric hindrance at the living chain ends,further preventing attacks on the polymer chain and thereby eliminating transesterification.The mechanism of temperature-regulated H-bonding catalysis was validated through nuclear magnetic resonance(NMR)titration experiments,H-bonding constant studies,and density functional theory(DFT)calculations.The NHC/TU-2(0.5:1)achieved stereoretention during the ROPs of L-LA and D-LA,affording stereoregular poly(L-lactide)(PLLA)and poly(D-lactide)(PDLA)with predicted molecular weights,narrow dispersity(D<1.13),less epimerization(P_(m)>0.99),and no coloration.The thermal properties of the synthesized PLLA,PDLA,and their stereocomplexes were studied by thermogravimetric analysis(TGA)and differential scanning calorimetry(DSC).Furthermore,cytotoxicity tests demonstrated that the PLLA synthesized with NHC/TU-2 was nontoxic.展开更多
The conventional method of fabricating hydrogels constantly confronts the conflict between elasticity and toughness,limiting their repetitive application.Achieving the desired elasticity through a simple and low-cost ...The conventional method of fabricating hydrogels constantly confronts the conflict between elasticity and toughness,limiting their repetitive application.Achieving the desired elasticity through a simple and low-cost approach is a significant challenge for hydrogels,particularly through rational molecular design.Here,low-hysteresis and high-toughness hydrogels are developed from the design of a new feature monomer,N-acryloylethylsemicarbazide(NACE).Based on a concept of“asymmetric Hbonding design”,the unique double and triple H-bonding of NACE can result in a novel asymmetric crosslinking polymer with alternating strong and weak H-bonding regions.The NACE is copolymerized with acrylamide(AM)to regulate the mechanical properties of hydrogel via H-bonding density.The P(NACE-AM)ionic hydrogels are obtained simply and rapidly via one-step photopolymerization without a chemical cross-linking agent.The P(NACE-AM)hydrogels combine superb mechanical elasticity and toughness,and excellent ionic conductivity,showing great potential as durable ionic conductive devices for wearable utilization.展开更多
A theoretical study on the blue-shifted H-bond N-H…O and red-shifted H-bond O-H…O in the complex HNO…H2O2 was conducted by employment of both standard and counterpoise-corrected methods to calculate the geometric s...A theoretical study on the blue-shifted H-bond N-H…O and red-shifted H-bond O-H…O in the complex HNO…H2O2 was conducted by employment of both standard and counterpoise-corrected methods to calculate the geometric structures and vibrational frequencies at the MP2/6-31G（d）, MP2/6-31 ＋ G（d,p）, MP2/6-311 ＋ ＋ G（d,p）, B3LYP/6-31G（d）, B3LYP/6-31 ＋G（d,p） and B3LYP/6-311 ＋ ＋G（d,p） levels. In the H-bond N-H…O, the calculated blue shift of N-H stretching frequency is in the vicinity of 120 cm^-1 and this is indeed the largest theoretical estimate of a blue shift in the X-H…Y H-bond ever reported in the literature. From the natural bond orbital analysis, the red-shifted H-bond O-H…O can be explained on the basis of the dominant role of the hyperconjugation. For the blue-shifted H-bond N-H…O, the hyperconjugation was inhibited due to the existence of significant electron density redistribution effect, and the large blue shift of the N-H stretching frequency was prominently due to the rehybridization of spn N-H hybrid orbital.展开更多
Self-healing materials have attracted considerable attention because of their improved safety, lifetime, energy efficiency and environmental impact. Supramolecular interactions have been extensively considered in the ...Self-healing materials have attracted considerable attention because of their improved safety, lifetime, energy efficiency and environmental impact. Supramolecular interactions have been extensively considered in the field of self-healing materials due to their excellent reversibility and sensitive responsiveness to environmental stimuli. However,development of a polymeric material with good mechanical performance as well as self-healing capacity is very challenging. In this study, we report a robust self-healing polyurethane(PU) elastomer polypropylene glycol-2-amino-5-(2-hydroxyethyl)-6-methylpyrimidin-4-ol(PPG-mUPy) by integrating ureidopyrimidone(UPy) motifs with a PPG segment with a well-defined architecture and microphase morphology.To balance the self-healing capacity and mechanical performance, a thermal-triggered switch of H-bonding is introduced. The quadruple H-bonded UPy dimeric moieties in the backbone induce phase separation to form a hard domain as well as enable further aggregation into microcrystals by virtue of the stacking interactions, which are stable in ambient temperature. This feature endows the PU with high mechanical strength. Meanwhile, a high healing efficiency can be realized, when the reversibility of the H-bond was unlocked from the stacking at higher temperature. An optimized sample PPG1000-mUPy50%with a good balance of mechanical performance(20.62 MPa of tensile strength) and healing efficiency(93% in tensile strength) was achieved. This strategy will provide a new idea for developing robust self-healing polymers.展开更多
Controlling dynamic molecular self-assembly to finely tune macroscopic properties offers chemical solutions to rational material design.Here we report that combining disulfide-mediated ring-opening polymerization with...Controlling dynamic molecular self-assembly to finely tune macroscopic properties offers chemical solutions to rational material design.Here we report that combining disulfide-mediated ring-opening polymerization withβ-sheet-like H-bonding self-assembly can drive a direct small-molecular assembly into a layered ionic network with precise architectural tunability and controllable functions as ion-transport membranes.This strategy enables a one-step evaporationinduced self-assembly from discrete small molecules to layered ionic networks with high crystallinity.The interlayer distances can be readily engineered with nanometer accuracy by varying the length of the oligopeptide side chain.The synergy of the layered structure and hydrophilic terminal groups facilitates the formation and ordering of interlayer water channels,endowing the resulting membranes with high efficiency in transporting ions.Moreover,the inherent dynamic nature of poly(disulfide)s allows chemical recycling to monomers under mild conditions.We foresee that the robust strategy of combining dynamic disulfide chemistry and noncovalent assembly can afford many opportunities in designing smart materials with unique functions and applications.展开更多
A novel Uralic(U)-rich linear-hyperbranched mono-methoxy poly(ethylene glycol)-hyperbranched polyglycerol-graft-Uralic(mPEG-HPG-g-U)nanoparticle(NP)was prepared as drug carrier for antitumor methotrexate(MTX).Due to t...A novel Uralic(U)-rich linear-hyperbranched mono-methoxy poly(ethylene glycol)-hyperbranched polyglycerol-graft-Uralic(mPEG-HPG-g-U)nanoparticle(NP)was prepared as drug carrier for antitumor methotrexate(MTX).Due to the H-bond interaction of U with MTX and hydrophobic interaction,this NP exhibited high drug loading efficiency of up to 40%,which was significantly higher than that of traditional NPs based on U-absent copolymers(<15%).In addition,MTX-loaded mPEG-HPG-g-U NPs also demonstrated an acidity-accelerated drug release behavior.展开更多
Coordination polymers(CPs) are emerging as the next generation of macromolecule materials in many industrial and technological applications,e.g.gas/humidity sensing.The design of CP-based sensors with high performance...Coordination polymers(CPs) are emerging as the next generation of macromolecule materials in many industrial and technological applications,e.g.gas/humidity sensing.The design of CP-based sensors with high performance and low cost is of significance,but this work is still in the infancy stage.In this contribution,a new one dimensional(1D) CP has been successfully synthesized by a simple solvent evaporation method at room temperature,namely [Co(DPP)(H_(2)O)_(2)]n·(TCA)2(H_(2)O)_(4)(named as Co-1,HTCA=3-thiophenezoic acid,DPP=1,3-di(4-pyridyl)propane).The Co-1 structure contains abundant H-bonding interactions,weaving it from 1D chain structure into three dimensional(3D) pillared-layer structure.As an impedimetric humidity sensing material,this CP exhibits short response time,small hysteresis,excellent repeatability,and good stability in the working range of 11%-97% relative humidity(RH).Furthermore,it also shows excellent performance in monitoring the moisture content of human finger skin.By analyzing the complex impedance spectra,the humidity sensing mechanism of Co-1 sensor was expounded at different RH ranges.展开更多
Previously we have shown that POCl3-mediated H-bonding-directed one-pot macrocyclization allows for the highly selective preparation of five-residue macrocycles as the predominant product with low yields of hexamers a...Previously we have shown that POCl3-mediated H-bonding-directed one-pot macrocyclization allows for the highly selective preparation of five-residue macrocycles as the predominant product with low yields of hexamers and an undetectable occurrence of both tetramers and heptamers.Replacing the interiorly arrayed methyl groups with ethyl groups in these 4-7 residue macrocycles alters the relative stability order among them.Specifically,ethoxy-substituted six-residue macrocycle,rather than pentamer,turns out to be computationally the most stable,suggesting that ethoxy-containing hexamer possibly can be formed as the major product under suitable conditions.We have investigated this possibility by varying reaction temperatures and concentrations,invariably affording pentamer as the major macrocycle with strained circular hexamers and highly strained circular heptamers produced in substantial amounts.This discrepancy can be reasonably explained on the basis of bimolecular reactions between two oligomers higher than monomers via kinetic simulations.In this scenario,the acyclic pentamer is kinetically "trapped" to undergo an intramolecular cyclization to yield circular pentamer,rather than to produce acyclic hexamer.As a result,acyclic hexamer precursor is generated largely from sterically demanding bimolecular reactions between a dimer and a tetramer,or between two trimers that are kinetically slower than the pentamer-producing chain-growth reactions.We additionally found that one-pot macrocyclization proceeds to the largest extent at 40 ℃,an intriguing finding that highlights the low reactivities of acid chloride and amine groups in these H-bond-enforced acyclic oligomeric intermediates.展开更多
Previously we have shown that POCl3-mediated H-bonding-directed one-pot macrocyclization allows for the highly selective preparation of five-residue macrocycles as the predominant product with low yields of hexamers a...Previously we have shown that POCl3-mediated H-bonding-directed one-pot macrocyclization allows for the highly selective preparation of five-residue macrocycles as the predominant product with low yields of hexamers and an undetectable occurrence of both tetramers and heptamers.Replacing the interiorly arrayed methyl groups with ethyl groups in these 4-7 residue macrocycles alters the relative stability order among them.Specifically,ethoxy-substituted six-residue macrocycle,rather than pentamer,turns out to be computationally the most stable,suggesting that ethoxy-containing hexamer possibly can be formed as the major product under suitable conditions.We have investigated this possibility by varying reaction temperatures and concentrations,invariably affording pentamer as the major macrocycle with strained circular hexamers and highly strained circular heptamers produced in substantial amounts.This discrepancy can be reasonably explained on the basis of bimolecular reactions between two oligomers higher than monomers via kinetic simulations.In this scenario,the acyclic pentamer is kinetically "trapped" to undergo an intramolecular cyclization to yield circular pentamer,rather than to produce acyclic hexamer.As a result,acyclic hexamer precursor is generated largely from sterically demanding bimolecular reactions between a dimer and a tetramer,or between two trimers that are kinetically slower than the pentamer-producing chain-growth reactions.We additionally found that one-pot macrocyclization proceeds to the largest extent at 40 ℃,an intriguing finding that highlights the low reactivities of acid chloride and amine groups in these H-bond-enforced acyclic oligomeric intermediates.展开更多
基金supported by the National Natural Science Foundation of China (21071004, 51173002)the Start-up Foundation and the young teacher’s research foundation of Anhui University of Science and Technology (11227, 2012QNZ08)the Research fund of Key Laboratory for Advanced Technology in Environmental Protection of Jiangsu Province (AE 201107)
文摘Solvothermal reactions of 4,4＇-oxybis（benzoic acid） （H2oba） with 1,3-dipyridyl benzene （1,3-dpb） produced a two-dimensional （2D） cadmium（Ⅱ） coordination polymer {[Cd（oba）（dpb）]·H2O}n （1）. The complex was characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group C2/c with a = 13.6692（9）, b = 25.9647（17）, c = 8.7912（6） , α = 125.0370（10）, γ = 2544.7（3）°, V = 2544.7（3） 3, C30H22N2O6Cd, Mr = 618.91, Dc =1.609 g/cm3, F（000） = 1248, μ = 0.904 mm-1 and Z = 4. The neighboring Cd（Ⅱ） ions are linked by oba2-anions and 1,3-dpb to form an infinitely 2D wavelike sheet, and two such 2D sheets are interlocked with each other by H-bonding to form a 2D → 2D structure. The adjacent two groups of interlocked structures are further linked to form a bilayer 2D supramolecular network by π-π interactions. In addition, the fluorescence property of 1 was also studied.
基金This work was financially supported by NSFC (Nos. 50073028, 29974036 and 20174047).
文摘A novel soluble regular ladder poly（benzoyl-3-aminopropyl） silsesquioxane （LPBAS） was facilely prepared under effective assistance of concerted H-bonding self-assembly of amido groups of side chains and silanol groups, respectively, of a new template monomer [1,3-bis（benzoyl-3-aminopropyl）-1,1,3,3-tetraethoxydisiloxane] （M）. The ordered ladder structure of LPBAS is manifested in： （1） the presence of two Bragg peaks representing the ladder width （d） and ladder thickness （t） in X-ray diffraction （XRD） pattern; （2） narrow base-line width （w = 6） of resonance absorption for -CH2SiO3/2 moiety in 29Si-NMR and （3） high glass transition temperature Tg = 1 12℃ in differential scanning calorimetry （DSC） analysis.
文摘The aim of this study was to develop an intravenous clarithromycin lipid emulsion(CLE)with good stability and excellent antibacterial activity. The CLE was prepared by the thinfilm dispersed homogenization method. The interaction between clarithromycin(CLA) and cholesteryl hemisuccinate(CHEMS) was confirmed by DSC, FT-IR and^1H NMR analysis. The interfacial drug loading, thermal sterilization, freeze–thaw stability, and in vitro and in vivo antibacterial activity were investigated systematically. DSC, FT-IR and^1H NMR spectra showed that CHEMS(CLA: CHEMS, M ratio 1:2) could interact with CLA through H-bonding and a hydrogen-bonded ion pair. The CHEMS was found necessary to maintain the stability of CLE.Ultracentrifugation showed that almost 88% CLA could be loaded into the interfacial layer.The optimized CLE formulation could withstand autoclaving at 121 °C for 10 min and remain stable after three freeze–thaw cycles. The in vitro susceptibility test revealed that the CLA–CHEMS ion-pair and CLE have similar activity to the parent drug against many different bacterial strains. The in vivo antibacterial activity showed that the ED50 of intravenous CLE was markedly lower than that of CLA solution administrated orally. CLE exhibited pronounced antibacterial activity and might be a candidate for a new nanocarrier for CLA with potential advantages over the current commercial formulation.
文摘A highly ordered m-phenylenediimino-bridged ladder polyhydrosiloxane （abbr. OLPHS） with Mn = 1.24 × 10^4 was synthesized stoichiometric hydrolysis and dehydrochlorination condensation reaction between Si-Cl and Si-OH bonds. The complete ladder structure of OLPHS has been confirmed by the following three data. Two characteristic Bragg＇s peaks representing the ladder width （w = 0.94 nm） and ladder thickness （t = 0.42 nm） were observed in XRD analysis, which are consistent with those calculated by molecular simulation. The very sharp absorption with a small half-peak width （w1/2 = 0.5 ppm） for [（-HN）HSiO2/2]n moiety of OLPHS in ^29Si NMR spectrum indicated presence of the complete ladder structure. As collateral evidence, a higher glass transition temperature （Tg = 105 ℃） is also recorded in the DSC measurement, implying the high stiffness of ladder chain of OLPHS.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.50073028,29974036,20174047).
文摘A novel soluble and reactive amide-bridged ladderlike polyhydrosiloxane （ALPHS） was first synthesized by an amido H-bonding self-assembled template. ALPHS with molecular weight M^-a = 18300 has very highly ordered ladderlike structure, which was confirmed by a sharp resonance absorption peak of [-Si（H）O2/2 ] moiety with the half peak width △1/2 〈 0.5 in^29Si-NMR spectrum. Presence of the reactive Si-H groups gives ALPHS an opportunity to further derive a variety of functional polymers by versatile Si-H reactions such as hydrosilylation, condensation, and so on.
文摘A novel, reactive amide-bridged ladder polyvinylsiloxane （abbr. LP） with Mn= 2.4×10^4 was synthesized for the first time by means of aryl amide H-bonding self-assembled template. The regularity of LP was characterized by the XRD, ^29Si NMR and DSC methods. XRD analysis demonstrated the ladder width w = 9.09A and the ladder thickness t = 3.89A, respectively, which are approximately consistent with the molecular simulation-calculated ones： w＇= 10.60A and t＇= 3.06A. ^29Si NMR displayed a resonance peak with small half peak width, △1/2 - 4 ppm, for the moiety [=Si（Vi）O2/2-]n of LP. Besides, as a collateral evidence, DSC measurement revealed a high glass transition temperature Tg = 225℃, suggesting high stiffness of the ladder main chain of LP.
文摘Design and preparation of highly efficient zeolite catalysts for gas-phase Beckmann rearrangement of cyclohexanone oxime to caprolactam are attractive but still challenging.Herein,we show a one-pot synthesis of silicalite-1 zeolite nanosheets with rich H-bonded silanols.The key to this success is the use of urea in the synthetic system.Catalytic tests of cyclohexanone oxime gas-phase Beckmann rearrangement show that the silicalite-1 zeolite nanosheets with H-bonded silanols exhibit higher selectivity for caprolactam and longer reaction lifetime than those of the conventional silicalite-1 zeolite.Theoretical simulations reveal that the ammonium decomposed by urea is a critical additive for the formation of H-bond silanols.Obviously,one-pot synthesis of silicalite-1 zeolite nanosheets with rich H-bonded silanols plus excellent catalytic performance in the Beckmann rearrangement offer a new opportunity for development of highly efficient zeolites for catalytic applications in the future.
基金This research was supported by the Key Subject Foundation of Jiangsu Province(S1109001)
文摘The title compound (C17H16O2, Mr = 252.30) crystallizes in the monoclinic system, space group P21/c with a = 11.5763(14), b = 11.0321(11), c = 11.5094(13) ?, β = 114.581(3)o, V = 1336.7(3) ?3 , Z = 4, Dc = 1.254 g/cm3, μ(MoKa) = 0.081 cm-1 and F(000) = 536.00. The final R and wR are 0.0527 and 0.1285, respectively for 3058 observed reflections (I > 2σ(I)). In the title molecule, two phenyl rings are rotated oppositely with respect to the central part C(1)–C(2)=C(3)– C(4) (plane 3) and the dihedral angle between them is 14.8o. The phenone O(1) atom deviates from plane 3 by 0.291 ?. In the crystal the molecules form H-bond chains of R2 (6) and R2 (5) types 1 1 along [001]. The molecule chains interacted through three cooperative C–H…O H-bonds (R3 (11)) 1 in the ‘bay area’ (Fig. 3), extending along [010] and forming layer (100). Between the layers, there exist C–H/π interactions along [101]. Studies on the cooperative C–H…O H-bonds R3 (11) in the 1 similar crystals are also presented.
基金supported by the National Key R&D Program of China(2022YFB3704900)the National Natural Science Foundation of China(22301207,21925107)+2 种基金the Natural Science Foundation of Jiangsu Province(BK20230506)the Natural Science Foundation of Jiangsu Higher Education Institutions(23KJB150031)the Collaborative Innovation Center of Suzhou Nano Science and Technology。
文摘Organocatalytic ring-opening polymerization(ROP)is a more sustainable approach for synthesizing renewable and biodegradable polymers compared to conventional metal-based catalysis.A key challenge in the field has been applying organocatalysis under the harsh conditions of industrial ROP while maintaining high activity and selectivity.Herein,we present an efficient N-heterocyclic carbene/thiourea binary organocatalyst system(NHC/TU-2)for the ROP of lactide(LA)at elevated temperatures,offering excellent control by almost completely suppressing transesterification and epimerization.It was found that NHC/TU-2 operates according to the imidate H-bonding catalysis model;however,its notable feature is that the strength of the H-bonding is regulated by temperature,enabling the activation of the monomers with high selectivity.Additionally,the large size of the NHC/TU-2 complex introduces steric hindrance at the living chain ends,further preventing attacks on the polymer chain and thereby eliminating transesterification.The mechanism of temperature-regulated H-bonding catalysis was validated through nuclear magnetic resonance(NMR)titration experiments,H-bonding constant studies,and density functional theory(DFT)calculations.The NHC/TU-2(0.5:1)achieved stereoretention during the ROPs of L-LA and D-LA,affording stereoregular poly(L-lactide)(PLLA)and poly(D-lactide)(PDLA)with predicted molecular weights,narrow dispersity(D<1.13),less epimerization(P_(m)>0.99),and no coloration.The thermal properties of the synthesized PLLA,PDLA,and their stereocomplexes were studied by thermogravimetric analysis(TGA)and differential scanning calorimetry(DSC).Furthermore,cytotoxicity tests demonstrated that the PLLA synthesized with NHC/TU-2 was nontoxic.
基金supported by the National Natural Science Foundation of China (52303006)the National Postdoctoral Science Foundation of China (2023M731012)+1 种基金the Key Science and Technology Project of Henan Province (232102230099)the Foundation of Henan Educational Committee (24A150015)。
文摘The conventional method of fabricating hydrogels constantly confronts the conflict between elasticity and toughness,limiting their repetitive application.Achieving the desired elasticity through a simple and low-cost approach is a significant challenge for hydrogels,particularly through rational molecular design.Here,low-hysteresis and high-toughness hydrogels are developed from the design of a new feature monomer,N-acryloylethylsemicarbazide(NACE).Based on a concept of“asymmetric Hbonding design”,the unique double and triple H-bonding of NACE can result in a novel asymmetric crosslinking polymer with alternating strong and weak H-bonding regions.The NACE is copolymerized with acrylamide(AM)to regulate the mechanical properties of hydrogel via H-bonding density.The P(NACE-AM)ionic hydrogels are obtained simply and rapidly via one-step photopolymerization without a chemical cross-linking agent.The P(NACE-AM)hydrogels combine superb mechanical elasticity and toughness,and excellent ionic conductivity,showing great potential as durable ionic conductive devices for wearable utilization.
基金Project supported by the National Natural Science Foundation of China （No. G20477043） and Knowledge Creative Program of Chinese Academy of Sciences （No. KJCX2-SW-H08）.
文摘A theoretical study on the blue-shifted H-bond N-H…O and red-shifted H-bond O-H…O in the complex HNO…H2O2 was conducted by employment of both standard and counterpoise-corrected methods to calculate the geometric structures and vibrational frequencies at the MP2/6-31G（d）, MP2/6-31 ＋ G（d,p）, MP2/6-311 ＋ ＋ G（d,p）, B3LYP/6-31G（d）, B3LYP/6-31 ＋G（d,p） and B3LYP/6-311 ＋ ＋G（d,p） levels. In the H-bond N-H…O, the calculated blue shift of N-H stretching frequency is in the vicinity of 120 cm^-1 and this is indeed the largest theoretical estimate of a blue shift in the X-H…Y H-bond ever reported in the literature. From the natural bond orbital analysis, the red-shifted H-bond O-H…O can be explained on the basis of the dominant role of the hyperconjugation. For the blue-shifted H-bond N-H…O, the hyperconjugation was inhibited due to the existence of significant electron density redistribution effect, and the large blue shift of the N-H stretching frequency was prominently due to the rehybridization of spn N-H hybrid orbital.
基金financially supported by the National Natural Science Foundation of China(51773131,51811530149and 51721091)the International S&T Cooperation Project of Sichuan Province(2017HH0034)
文摘Self-healing materials have attracted considerable attention because of their improved safety, lifetime, energy efficiency and environmental impact. Supramolecular interactions have been extensively considered in the field of self-healing materials due to their excellent reversibility and sensitive responsiveness to environmental stimuli. However,development of a polymeric material with good mechanical performance as well as self-healing capacity is very challenging. In this study, we report a robust self-healing polyurethane(PU) elastomer polypropylene glycol-2-amino-5-(2-hydroxyethyl)-6-methylpyrimidin-4-ol(PPG-mUPy) by integrating ureidopyrimidone(UPy) motifs with a PPG segment with a well-defined architecture and microphase morphology.To balance the self-healing capacity and mechanical performance, a thermal-triggered switch of H-bonding is introduced. The quadruple H-bonded UPy dimeric moieties in the backbone induce phase separation to form a hard domain as well as enable further aggregation into microcrystals by virtue of the stacking interactions, which are stable in ambient temperature. This feature endows the PU with high mechanical strength. Meanwhile, a high healing efficiency can be realized, when the reversibility of the H-bond was unlocked from the stacking at higher temperature. An optimized sample PPG1000-mUPy50%with a good balance of mechanical performance(20.62 MPa of tensile strength) and healing efficiency(93% in tensile strength) was achieved. This strategy will provide a new idea for developing robust self-healing polymers.
基金This work was supported by the National Natural Science Foundation of China(grant nos.22025503,21790361,21788102,and 21871084)Shanghai Municipal Science and Technology Major Project(grant no.2018SHZDZX03)+2 种基金the Fundamental Research Funds for the Central Universities,the Programme of Introducing Talents of Discipline to Universities(grant no.B16017)Program of Shanghai Academic/Technology Research Leader(grant no.19XD1421100),Science and Technology Commission of Shanghai Municipality(grant no.21JC1401700)the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study(grant no.SN-ZJU-SIAS-006).The authors thank the Research Center of Analysis and Test of East China University of Science and Technology for help on the material characterization.
文摘Controlling dynamic molecular self-assembly to finely tune macroscopic properties offers chemical solutions to rational material design.Here we report that combining disulfide-mediated ring-opening polymerization withβ-sheet-like H-bonding self-assembly can drive a direct small-molecular assembly into a layered ionic network with precise architectural tunability and controllable functions as ion-transport membranes.This strategy enables a one-step evaporationinduced self-assembly from discrete small molecules to layered ionic networks with high crystallinity.The interlayer distances can be readily engineered with nanometer accuracy by varying the length of the oligopeptide side chain.The synergy of the layered structure and hydrophilic terminal groups facilitates the formation and ordering of interlayer water channels,endowing the resulting membranes with high efficiency in transporting ions.Moreover,the inherent dynamic nature of poly(disulfide)s allows chemical recycling to monomers under mild conditions.We foresee that the robust strategy of combining dynamic disulfide chemistry and noncovalent assembly can afford many opportunities in designing smart materials with unique functions and applications.
基金This work was supported by the National Key Basic Research Program of China(2011CB606202)National Natural Science Foundation of China(Grant Nos.21374085,21174110 and 51303137)the Fundamental Research Funds for the Central Universities(2042014kf0193).
文摘A novel Uralic(U)-rich linear-hyperbranched mono-methoxy poly(ethylene glycol)-hyperbranched polyglycerol-graft-Uralic(mPEG-HPG-g-U)nanoparticle(NP)was prepared as drug carrier for antitumor methotrexate(MTX).Due to the H-bond interaction of U with MTX and hydrophobic interaction,this NP exhibited high drug loading efficiency of up to 40%,which was significantly higher than that of traditional NPs based on U-absent copolymers(<15%).In addition,MTX-loaded mPEG-HPG-g-U NPs also demonstrated an acidity-accelerated drug release behavior.
基金financially supported by the Tianjin Municipal Education Commission (No. 2018KJ271)National Natural Science Foundation of China (NSFC, No. 21601094, 21401139, and 21271139)。
文摘Coordination polymers(CPs) are emerging as the next generation of macromolecule materials in many industrial and technological applications,e.g.gas/humidity sensing.The design of CP-based sensors with high performance and low cost is of significance,but this work is still in the infancy stage.In this contribution,a new one dimensional(1D) CP has been successfully synthesized by a simple solvent evaporation method at room temperature,namely [Co(DPP)(H_(2)O)_(2)]n·(TCA)2(H_(2)O)_(4)(named as Co-1,HTCA=3-thiophenezoic acid,DPP=1,3-di(4-pyridyl)propane).The Co-1 structure contains abundant H-bonding interactions,weaving it from 1D chain structure into three dimensional(3D) pillared-layer structure.As an impedimetric humidity sensing material,this CP exhibits short response time,small hysteresis,excellent repeatability,and good stability in the working range of 11%-97% relative humidity(RH).Furthermore,it also shows excellent performance in monitoring the moisture content of human finger skin.By analyzing the complex impedance spectra,the humidity sensing mechanism of Co-1 sensor was expounded at different RH ranges.
基金supports by A*STAR BMRC Research Consortia(R-143-000- 388-305 to H.Z.)Environment and Water Industry Development Council and Economic Development Board(SPORE,COY-15-EWI-RCFSA/N197-1 to H.Z.).
文摘Previously we have shown that POCl3-mediated H-bonding-directed one-pot macrocyclization allows for the highly selective preparation of five-residue macrocycles as the predominant product with low yields of hexamers and an undetectable occurrence of both tetramers and heptamers.Replacing the interiorly arrayed methyl groups with ethyl groups in these 4-7 residue macrocycles alters the relative stability order among them.Specifically,ethoxy-substituted six-residue macrocycle,rather than pentamer,turns out to be computationally the most stable,suggesting that ethoxy-containing hexamer possibly can be formed as the major product under suitable conditions.We have investigated this possibility by varying reaction temperatures and concentrations,invariably affording pentamer as the major macrocycle with strained circular hexamers and highly strained circular heptamers produced in substantial amounts.This discrepancy can be reasonably explained on the basis of bimolecular reactions between two oligomers higher than monomers via kinetic simulations.In this scenario,the acyclic pentamer is kinetically "trapped" to undergo an intramolecular cyclization to yield circular pentamer,rather than to produce acyclic hexamer.As a result,acyclic hexamer precursor is generated largely from sterically demanding bimolecular reactions between a dimer and a tetramer,or between two trimers that are kinetically slower than the pentamer-producing chain-growth reactions.We additionally found that one-pot macrocyclization proceeds to the largest extent at 40 ℃,an intriguing finding that highlights the low reactivities of acid chloride and amine groups in these H-bond-enforced acyclic oligomeric intermediates.
文摘Previously we have shown that POCl3-mediated H-bonding-directed one-pot macrocyclization allows for the highly selective preparation of five-residue macrocycles as the predominant product with low yields of hexamers and an undetectable occurrence of both tetramers and heptamers.Replacing the interiorly arrayed methyl groups with ethyl groups in these 4-7 residue macrocycles alters the relative stability order among them.Specifically,ethoxy-substituted six-residue macrocycle,rather than pentamer,turns out to be computationally the most stable,suggesting that ethoxy-containing hexamer possibly can be formed as the major product under suitable conditions.We have investigated this possibility by varying reaction temperatures and concentrations,invariably affording pentamer as the major macrocycle with strained circular hexamers and highly strained circular heptamers produced in substantial amounts.This discrepancy can be reasonably explained on the basis of bimolecular reactions between two oligomers higher than monomers via kinetic simulations.In this scenario,the acyclic pentamer is kinetically "trapped" to undergo an intramolecular cyclization to yield circular pentamer,rather than to produce acyclic hexamer.As a result,acyclic hexamer precursor is generated largely from sterically demanding bimolecular reactions between a dimer and a tetramer,or between two trimers that are kinetically slower than the pentamer-producing chain-growth reactions.We additionally found that one-pot macrocyclization proceeds to the largest extent at 40 ℃,an intriguing finding that highlights the low reactivities of acid chloride and amine groups in these H-bond-enforced acyclic oligomeric intermediates.
