A 3-D supramolecular framework, [Er（pybz）2（Hnds）（H2O）2]·H2O （1, Hpybz = 4- pyridin-4-yl-benzoic acid, H2nds = naphthalene-1,5-disulfonic acid）, based on lanthanide ions and mixed ligands has been hydrothe...A 3-D supramolecular framework, [Er（pybz）2（Hnds）（H2O）2]·H2O （1, Hpybz = 4- pyridin-4-yl-benzoic acid, H2nds = naphthalene-1,5-disulfonic acid）, based on lanthanide ions and mixed ligands has been hydrothermally synthesized. The structure was determined by single-crystal X-ray diffraction and further characterized by IR, elemental analysis and thermogravimetric analysis. Compound 1 crystallizes in the monoclinic system, space group P21/n with a = 9.849（2）, b = 22.526（5）, c = 17.167（4） A, β =105.461（4）° and V = 3670.9（2） A^3. In 1, two seven-coordinated Er^3＋ ions are bridged by two pybz^- ligands to form a dimeric [Er2（COO）2] unit, which is further orderly linked by carboxyl of pybz^-ligand to obtain a 1-D chain running along the a axis. Interestingly, significant H-bonding and π-π stacking interactions link the neighboring parallel chains leading to a 3-D supramolecular network structure which displays 1-D rhombus open channels （17.2A× 22.5A）.展开更多
Based on the crystal structures of two cucurbit[6]uril/calix[n]arene-based supramolecular frameworks reported by Long and co-workers,we further investigated the interactions of cucurbit[6]uril with 4-sulfocalix[4]aren...Based on the crystal structures of two cucurbit[6]uril/calix[n]arene-based supramolecular frameworks reported by Long and co-workers,we further investigated the interactions of cucurbit[6]uril with 4-sulfocalix[4]arene and 4-sulfocalix[6]arene using ^(1)H NMR spectroscopy and isothermal titration calorimetry(ITC),respectively.Moreover,solid fluorescent materials were prepared via the adsorption of fluorescent dyes by these porous supramolecular frameworks,which exhibit a selective response to certain volatile organic compounds.展开更多
Curcurbit[n]uril(Q[n])-based supramolecular frameworks(QSFs) constructed from the outer surface interaction of Q[n]s(OSIQ) have the characteristic of simplicity,diversity and modulability.Their simplicity is reflected...Curcurbit[n]uril(Q[n])-based supramolecular frameworks(QSFs) constructed from the outer surface interaction of Q[n]s(OSIQ) have the characteristic of simplicity,diversity and modulability.Their simplicity is reflected in their simple composition and preparation methods used for QSFs.The diversity of supramolecular organic frameworks(SOFs) is reflected in the synthesis methods and structural characteristics of the as-obtained QSFs,as well as the variety of structural directing agents and basic building blocks used to prepare QSFs.The modulability is reflected by the controllable channel size in the QSFs,which can be adjusted using different sizes of Q[n]s.In this work,the first re ported cucurbituril Q[6]was selected as the basic building block and three Q[6]-based su p ramolecular frameworks were obtained from aqueous HCl solutions in the presence of [CdCl_(4)]^(2-)respectively.The OSIQs are the main driving forces for the formation of these frameworks.This study shows the diversity of the QSFs.展开更多
A neoteric organic-inorganic hybrid Co-substituted phosphotungstate H6{[Co(en)2(OAc)2]2[Co4(H2 O)2(PW9 O34)2]}?2 H2 en?36 H2 O(1, en = enthylenediamine) has been made under hydrothermal conditions and characterized by...A neoteric organic-inorganic hybrid Co-substituted phosphotungstate H6{[Co(en)2(OAc)2]2[Co4(H2 O)2(PW9 O34)2]}?2 H2 en?36 H2 O(1, en = enthylenediamine) has been made under hydrothermal conditions and characterized by IR spectrum, thermogravimetric analysis, diffuse-reflectance spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction and cyclic voltammetry, respectively. Crystal data for 1: monoclinic, P21/c, a = 18.2234(12), b = 15.3696(9), c = 20.1706(17) ?, β = 106.563(8)°, V = 5415.1(7) ?3, Z = 2, Mr = 6072.30, Dc = 3.724 g/cm3, μ = 20.087 mm-1, F(000) = 5540, R = 0.0585, w R = 0.1543 and S = 1.024. Single-crystal X-ray structure analysis reveals that compound 1 exhibits a 3-D supramolecular framework via H-bonding interactions, in which the discrete Co-complex is modified by two types of organic ligands, en and acetate. In addition, the adsorption experiments demonstrate compound 1 possesses a remarkable capability for scavenging of methylene blue.展开更多
Supramolecular frameworks(SMFs)are famous for their fascinating structure and abundant porosity;however,poor crystalline stability in water severely limits their applications.Herein,an anchoringpolymerization strategy...Supramolecular frameworks(SMFs)are famous for their fascinating structure and abundant porosity;however,poor crystalline stability in water severely limits their applications.Herein,an anchoringpolymerization strategy was developed under mild conditions to modulate the surface microenvironment of SMFs.The process-tracking experiment demonstrated that toluene diisocyanate(TDI)was anchored on the surface of SMF-BDC-NH_(2)before chain polymerization was initiated between TDI by introducing trace amounts of water.The glue-like polyurea armor on the surface of SMF-BDC-NH_(2)@PTDI endowed it with a water contact angle of 131.3°,and it can maintain good crystallinity and a porous structure even when immersed in water for 24 hours.SMF-BDC-NH_(2)@PTDI was proved to selectively adsorb cationic dyes,and no significant loss was detected after 5 runs,whereas the pristine material lost crystallinity and adsorption performance immediately after regeneration.The dynamic breakthrough experiment showed that SMF-BDC-NH_(2)@PTDI had an adsorption capacity of 124 mg g^(-1),positioning it among the best materials of its kind.Suitable pore size and charge interactions are proved to be the main driving forces for selective adsorption.This work may open a path to modulation of the surface microenvironment of SMFs to maintain crystalline stability and enable advanced applications in water treatment.展开更多
Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability...Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability.However,precise control and tune the pore size of such frameworks still remains a significant challenge to date.In this study,we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block.First,a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization.Then 2-ureido-4[1H]-pyrimidinone(Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization.Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units,well-ordered supramolecular polymer frameworks were readily obtained.Notably,the pore size was dependent on the chain length of the polyisocyanide arms.Precisely control the chain length of polyisocyanide arms,supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved.These frameworks,with tunable and large pore apertures,demonstrated exceptional capabilities in encapsulating enzymes of different sizes,such as lipase(TL),horseradish peroxidase(HRP),and glucose oxidase(GOx).The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability.Moreover,the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes,enabling efficient dual-enzyme cascade reactions.展开更多
Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments re...Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature.One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice,which improves by 40%compared with the highest value of the reported SOFs.In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrugresistant MDR A549/ADR tumor cells to realize intracellular delivery,leading to enhanced antitumor efficacy.Moreover,it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism.As the first examples that undergo roomtemperature reversible assembly and disassembly,the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.展开更多
Frameworks utilizing cucurbit[n]uril-based chemistry build on the rapid developments in the fields of metal-organic frameworks(MOFs),covalent-organic frameworks(COFs)and supramolecular organic frameworks(SOFs),and as ...Frameworks utilizing cucurbit[n]uril-based chemistry build on the rapid developments in the fields of metal-organic frameworks(MOFs),covalent-organic frameworks(COFs)and supramolecular organic frameworks(SOFs),and as porous materials have found broad applications in heterogeneous catalysis,adsorption and ion exchange as well as other fields.Cucurbit[n]urils(Q[n]s)are suitable as the basic building blocks used for the construction of new Q[n]-based frameworks due to their special structural characteristics including the positive electrostatic potential of the outer surface,the negative portal carbonyl groups and the near neutral potential of the cavity.Herein,summaries of cucurbit[n]uril-based supramolecular frameworks assembled through outer surface interactions and cucurbit[n]uril/metal ion complex-based frameworks are discussed,and this is followed by a review of Q[n]-based frameworks assembled using the structural characteristics associated with the cavity of Q[n]s,i.e.host-vip inclusion chemistry.These assembled Q[n]-based frameworks can be catalogued as(1)simple host-vip inclusion complexes,(2)host-vip inclusion supramolecular polymers,(3)host-vip exclusion complexes or polymers and(4)coordination products of the host-vip inclusion complexes with metal ions.The design and construction of Q[n]-based frameworks via host-vip inclusion chemistry will undoubtedly enrich this new research direction in Q[n]chemistry,and will lead to multiple new applications.展开更多
Supramolecular nanocages with inner cavities have attracted increasing attention due to their fascinating molecular aesthetics and vast number of potential applications.Even though a wide array of discrete supramolecu...Supramolecular nanocages with inner cavities have attracted increasing attention due to their fascinating molecular aesthetics and vast number of potential applications.Even though a wide array of discrete supramolecular cages with precisely designed sizes and shapes have been established,the controlled assembly of higher-order supramolecular frameworks from discrete molecular entities still represents a formidable challenge.In this work,a novel metallo-organic cage[Zn_(12)L_(4)]was assembled based on a triphenylene-cored hexapod terpyridine ligand.Synchotron X-ray analysis revealed a pair of enantiomeric cages in the crystal with flexible ligands twisted clockwise or anticlockwise due to steric hindrance in the structure.Interestingly,due to the strongπ-πintermolecular interaction between triphenylene units,a controlled hierarchical packing of sphere-like cages in the crystal was established having a sparse packing mode with huge channels of around 3.6 nm diameter.This research sheds light on the design of strongπ-πinteractions in supramolecular hierarchical packing and materials science.展开更多
The selective oxidation of organic sulfides is a pivotal step in the preparation of sulfoxides that can act as synthetic intermediates when preparing fine chemicals,bioactive molecules,and asymmetric catalysis ligands...The selective oxidation of organic sulfides is a pivotal step in the preparation of sulfoxides that can act as synthetic intermediates when preparing fine chemicals,bioactive molecules,and asymmetric catalysis ligands.To construct high-performance heterogeneous catalysts for sulfide-sulfoxide transformations,herein,we designed and synthesized a supramolecular porous catalyst based onε-Keggin polyoxometalates(POMs),TBA_(2)H_(2)[Zn_(4)(im)(Him)_(2)][ε-PMo_(8)VMo_(4)VIO_(40)]·3H_(2)O(1,Him=1H-imidazole).Single-crystal X-ray diffraction analysis indicates that the porous framework of 1 can be obtained via the supramolecular stacking of one-dimensional helical chains alternately linked by Zn_(4)-ε-Keggin clusters and Him ligands.During the selective oxidation of methyl phenyl sulfide to methyl phenyl sulfoxide(MPSO),compound 1 achieved a>99%yield toward MPSO and 90.3%oxidant utilization efficiency within 10 min.The corresponding turnover frequency(TOF),expressing catalytic activity,was up to 1200 h^(-1).The catalyst also demonstrated extensive substrate tolerance during catalysis,and the corresponding yields of sulfoxides were satisfactory when only 1.2 equivalents of oxidant were used.Besides this,1 can also effectively degrade a sulfur mustard simulant(2-chloroethyl ethyl sulfide)to the nontoxic product 2-chloroethyl ethyl sulfoxide within 10 min at room temperature,with an oxidant utilization efficiency of up to 94.5%.Importantly,the excellent catalytic activity of compound 1 was also proven via comparison with an analogous 3D compound 2(TOF=800 h^(-1)at full MPS conversion),TBAH_(2)[K(Him)(im)][Zn_(4)(Him)(Hip)][ε-PMo_(8)VMo_(4)VIO_(40)](Hip=4-(1H-imidazol-2-yl)-pyridine),which was covalently assembled from one-dimensional Zn_(4)-ε-Keggin POM chains and metal-organic units.Moreover,the truly heterogeneous nature of 1 and 2 was confirmed via cycling and hot-filtration experiments,and their structural stability was verified based on Fourier-transform infrared spectra and powder X-ray diffractometry(PXRD)patterns.展开更多
Systematicly tuning the porosities of porous materials is crucial for targeted gas mixture separation,yet it remains a longstending challenge.As a common strategy,altering the phenylene ring count in the organic build...Systematicly tuning the porosities of porous materials is crucial for targeted gas mixture separation,yet it remains a longstending challenge.As a common strategy,altering the phenylene ring count in the organic building units has been exploited to adjust pore apertures in metal organic frameworks(MOFs)and covalent organic frameworks(COFs),re sulting in only a stepwise pore size variation of approximately 2.8?.Unlike MOFs and COFs,the porosities for supramolecular assembly frameworks are highly dependent on the packings of the molecular building units in the lattice.The above strategy cannot be applied to supramolecular assembly frameworks and other strategies are required to adjust pore apertures in supramolecular frameworks,especially to achieve porous materials with the optimal pore size for D_(2)/H_(2)separation(~3Å).Here,we successfully modulate the poro sity of supramolecular frameworks of[Co^(Ⅱ)_(12)Co^(Ⅲ)_(8)(μ_(3)-OH)_(24)(X)]^(11+)clusters(L=mono-deprotonated 1-iminoisoindole-3-amine,X=ClO_(4)-or Cl^(-))by controlling the duration of self-assembly processes.By simply adjusting the reaction time,we obtain three[Co^(Ⅱ)_(12)Co^(Ⅲ)_(8)(μ_(3)-OH)_(24)(X)]^(11+)supramolecular frameworks:[Co_(12)^(Ⅱ)Co_(8)^(Ⅲ)(μ^(3)-OH)_(24)(ClO_(4))L_(12))]·(Cl)_(4)·(HCO_(2))_(7)(1),[Co_(12)^(Ⅱ)Co_(8)^(Ⅲ)L_(12)(μ^(3)-OH)_(24)(Cl)]·(ClO_(4))4·(Cl)_(6)·(HCO_(2))·(H_(2)O)10(2),and[Co_(12)^(Ⅱ)Co_(8)^(Ⅲ)L_(12)(μ^(3)-OH)_(24)(Cl)]·(Cl)_(11)·(H_(2)O)12(3).The different stacking patterns of the[Co^(Ⅱ)_(12)Co^(Ⅲ)_(8)(μ_(3)-OH)_(24)(X)]^(11+)clusters in these frameworks lead to significantly varied stabilities and porosities.Compound 1 exhibits permanent porosity with interconnected channels and maintains stability under harsh conditions.In contrast,compound 2 is nearly nonporous,and compound 3 becomes unstable upon desolvation.The pores of compound 1 show higher affinity to D_(2)than H_(2),and the pore aperture diameter of compound 1(~3.06Å)meets the optimal porosity for D_(2)/H_(2)separation.Consequently,compound 1 demonstrates moderate D_(2)/H_(2)separation at 77 K(retention time:~7 min/g for D_(2)/H_(2)/Ne(10/10/80 vol%)in a flow of 5 mL/min).These results provide a new strategy to tune the porosities of porous supramolecular materials for target gas mixture separation.展开更多
A series of Cd(Ⅱ)coordination complexes with an elongated 2,4-dipyridyl-type building block trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene(bpe)and different dicarboxylate ligands have been presented.Generally,bpe shows th...A series of Cd(Ⅱ)coordination complexes with an elongated 2,4-dipyridyl-type building block trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene(bpe)and different dicarboxylate ligands have been presented.Generally,bpe shows the unidentate coordination mode and serves as the terminal pendant,whereas the dicarboxylate ligands display various binding fashions to interlink the metal centers to form 1-D comb-like chain,ribbon,and fishbone arrays,as well as 2-D 44 and 4.82 layered networks.Notably,the bpe building block is also involved in secondary interactions such as hydrogen bonding and aromatic stacking to construct the resulting supramolecular architectures.Thermal stability of these complexes has been studied by TG-DTA technique.展开更多
Porous supramolecular frameworks based on metal-organic cages(MOCs)usually have poor structural stability after activation.This issue narrows the scope of their potential applications,particularly for the inclusion of...Porous supramolecular frameworks based on metal-organic cages(MOCs)usually have poor structural stability after activation.This issue narrows the scope of their potential applications,particularly for the inclusion of vip molecules that demand high porosity.Herein,the authors have reported the stabilization of a mesoporous zirconium MOC-based supramolecular framework with an in situ catalytic polymerization strategy.Due to the passivation effect imparted by this strategy,the introduced polymer is primarily distributed on the surface of the crystals,which results in the hybrid material retaining its crystallinity and permanent porosity.A preliminary application of this type of stabilized mesoporous supramolecular framework shows that among MOC-based supramolecular frameworks,it has the highest high-pressure methane uptake.Such a facile strategy may provide a general way to stabilize fragile porous materials and facilitate exploration of their potential applications.展开更多
A microporous supramolecular framework with high water and thermal stability can selectively absorb water molecules over methanol or ethanol due to the suitable channels.The model separation test on columns shows that...A microporous supramolecular framework with high water and thermal stability can selectively absorb water molecules over methanol or ethanol due to the suitable channels.The model separation test on columns shows that an ultra-pure ethanol(99.9%)can be obtained from the mixture of ethanol/water(95:5).Additionally,after refluxing the desolvated sample in 95%ethanol at 60℃for 5 h,the purity of ethanol rises up to 97.43%,which is obviously higher than 96.56%for 4 A molecular sieves.展开更多
Accompanied by solid-state structural phase transitions,the switchable molecular dynamics(MD)and order-disorder transformation of(i-PrNHMe2)^(+)cation embedded in a deformable{[Ni(NCS)_(6)]^(4-)}_(∞)supramolecular fr...Accompanied by solid-state structural phase transitions,the switchable molecular dynamics(MD)and order-disorder transformation of(i-PrNHMe2)^(+)cation embedded in a deformable{[Ni(NCS)_(6)]^(4-)}_(∞)supramolecular framework are in-depth investigated by variable-temperature tests of single-crystal X-ray diffraction,dielectric measurement,and MD simulation.Interestingly,it is found that the confined swinging or flipping of the(i-PrNHMe_(2))^(+)cation as a whole is assisted by a synergistic change of its torsion angle.This research provides a helpful insight into the solid-state MD of moderate-sized quasi-spherical molecules/ions that feature a flexible inner core.展开更多
Two-dimensional(2D) materials have been demonstrated to exhibit unique properties originating from its 2D nature. In recent years, the construction of 2D materials has become a topic of great interest. This article su...Two-dimensional(2D) materials have been demonstrated to exhibit unique properties originating from its 2D nature. In recent years, the construction of 2D materials has become a topic of great interest. This article summarizes the recent advance of 2D supramolecular organic frameworks(SOFs) which are homogeneously constructed in solution phase through self-assembly of rationally designed building blocks. These 2D SOFs are soluble and still maintain stable network structures in solutions, which exhibit uniqueness not only in structures but also in properties. In this concise review, the SOFs-related background is briefly introduced firstly, followed by outlining the research progress of soluble 2D SOFs from the perspective of monomer design, assembly, and structural characterization.The article ends with a personal outlook on the future development of this new class of supramolecular polymers.展开更多
Ru(bpy)3]2+-cored supramolecular organic framework SMOF-1, assembled from a [Ru(bpy)3]2+-derived hexaarmed molecule and cucurbit[8]uril, has been demonstrated to heterogeneously catalyze visible light-induced reductio...Ru(bpy)3]2+-cored supramolecular organic framework SMOF-1, assembled from a [Ru(bpy)3]2+-derived hexaarmed molecule and cucurbit[8]uril, has been demonstrated to heterogeneously catalyze visible light-induced reduction of phenyl, benzyl, 2-phenylethyl and 3-phenylpropyl azides in acetonitrile to produce the corresponding amines in good to high yields. For the last two kinds of azides that bear a CO2Me group at the para-position of the benzene ring, cascade reactions take place to generate the corresponding lactams in high yields. Compared with homogeneous control [Ru(bpy)3]Cl2, SMOF-1 exhibits remarkably increased photocatalysis activity as a result of synergistic effect of the [Ru(bpy)3]2+ units that form cubic cages to host the azide molecules and related intermediates. Moreover, SMOF-1 displays high recyclability and considerable photocatalysis activity after 3 to 12 runs.展开更多
Four water-soluble porous supramolecular organic framework drug delivery systems（sof-DDSs） have been used to adsorb doxorubicin（DOX） in water at physiological pH of 7.4,which is driven exclusively by hydrophobicit...Four water-soluble porous supramolecular organic framework drug delivery systems（sof-DDSs） have been used to adsorb doxorubicin（DOX） in water at physiological pH of 7.4,which is driven exclusively by hydrophobicity.The resulting complexes DOX@SOFs are formed instantaneously upon dissolving the components in water.The drug-adsorbed sof-DDSs can undergo plasm circulation with important maintenance of the drug and overcome the multidrug resistance of human breast MCF-7/Adr cancer cells.DOX is released readily in the cancer cells due to the protonation of its amino group in the acidic medium of cancer cells.In vitro and in vivo experiments reveal that the delivery of SOF-a-d remarkably improve the cytotoxicity of DOX for the MCF-7/Adr cells and tumors,leading to 13-19-fold reduction of the 1C_（50）values as compared with that of DOX.This new sof-DDSs strategy omits the indispensable loading process required by most of reported nano-scaled carriers for neutral hydrophobic chemotherapeutic agents,and thus should be highly valuable for future development of low-cost delivery systems.展开更多
Water-soluble three-dimensional porous supramolecular organic frameworks（SOFs） have been demonstrated as a new generation of homogeneous polycationic platforms for anti-cancer drug delivery.The new SOF drug delivery...Water-soluble three-dimensional porous supramolecular organic frameworks（SOFs） have been demonstrated as a new generation of homogeneous polycationic platforms for anti-cancer drug delivery.The new SOF drug delivery systems（sof-DDSs） can adsorb dianionic pemetrexed（PMX）,a clinically used chemotherapeutic agent instantaneously upon dissolving in water,which is driven by both electrostatic attraction and hydrophobicity.The in situ-prepared PMX@SOFs are highly stable and can avoid important release of the drug during plasm circulation and overcome the multidrug resistance of human breast MCF-7/Adr cancer cells to enter the cancer cells.Acidic microenvironment of cancer cells promotes the release of the drug in cancer cells.Both in vitro and in vivo studies have revealed that sofDDSs considerably improve the treatment efficacy of PMX,leading to 6-12-fold reduction of the IC50 values,as compared with that of PMX alone.The new drug delivery strategy omits the loading process required by most of reported nanoparticle-based delivery systems and thus holds promise for future development of low-cost drug delivery systems展开更多
Here we use nor-seco-cucurbit[10]uril(ns-CB[10]) based ternary complexation to construct [5]rotaxane,linear supramolecular dynamic rotaxane polymers and cubic 3D supramolecular organic framework.A [5]rotaxane is const...Here we use nor-seco-cucurbit[10]uril(ns-CB[10]) based ternary complexation to construct [5]rotaxane,linear supramolecular dynamic rotaxane polymers and cubic 3D supramolecular organic framework.A [5]rotaxane is constructed by ns-CB[10], TMe CB[6] and short linear derivatives of 4,4'-bipyridinium(M2). ns-CB[10], CB[7] and long linear derivatives of 4,4'-bipyridinium(M3) self-assemble into a linear supramolecular dynamic rotaxane polymer. ns-CB[10] and tetracationic tetrahedral monomer selfassemble and form a three-dimensional supramolecular organic framework. The above results demonstrate that ns-CB[10]-based ternary complexation is a versatile platform to build various supramolecular systems.展开更多
基金supported by the National Natural Science Fund for Distinguished Young Scholars of China (No. 20725101)the 973 Program (No. 2006CB932904)+2 种基金the NSF of Fujian Province (Nos. E0510030 and 2008F3120)the Knowledge Innovation Program of CAS (No. KJCX2.YW.H01)NNSFC (No. 20521101)
文摘A 3-D supramolecular framework, [Er（pybz）2（Hnds）（H2O）2]·H2O （1, Hpybz = 4- pyridin-4-yl-benzoic acid, H2nds = naphthalene-1,5-disulfonic acid）, based on lanthanide ions and mixed ligands has been hydrothermally synthesized. The structure was determined by single-crystal X-ray diffraction and further characterized by IR, elemental analysis and thermogravimetric analysis. Compound 1 crystallizes in the monoclinic system, space group P21/n with a = 9.849（2）, b = 22.526（5）, c = 17.167（4） A, β =105.461（4）° and V = 3670.9（2） A^3. In 1, two seven-coordinated Er^3＋ ions are bridged by two pybz^- ligands to form a dimeric [Er2（COO）2] unit, which is further orderly linked by carboxyl of pybz^-ligand to obtain a 1-D chain running along the a axis. Interestingly, significant H-bonding and π-π stacking interactions link the neighboring parallel chains leading to a 3-D supramolecular network structure which displays 1-D rhombus open channels （17.2A× 22.5A）.
基金the financial support of National Natural Science Foundation of China(Nos.51663005,21761007 and21871064)Science and Technology Plan Project of Guizhou Province(Nos.20175788 and 20185781)+2 种基金the Creative Research Groups of Guizhou Provincial Education Department(No.2017028)the Innovation Program for High-level Talents of Guizhou Province(No.20165657)“Chun-Hui” Fund of Chinese Ministry of Education(No.Z2017005)。
文摘Based on the crystal structures of two cucurbit[6]uril/calix[n]arene-based supramolecular frameworks reported by Long and co-workers,we further investigated the interactions of cucurbit[6]uril with 4-sulfocalix[4]arene and 4-sulfocalix[6]arene using ^(1)H NMR spectroscopy and isothermal titration calorimetry(ITC),respectively.Moreover,solid fluorescent materials were prepared via the adsorption of fluorescent dyes by these porous supramolecular frameworks,which exhibit a selective response to certain volatile organic compounds.
基金the financial support of the National Natural Science Foundation of China(Nos.21761007,51663005 and 21871064)Science and Technology Plan Project of Guizhou Province(Nos.20175788 and 20185781)。
文摘Curcurbit[n]uril(Q[n])-based supramolecular frameworks(QSFs) constructed from the outer surface interaction of Q[n]s(OSIQ) have the characteristic of simplicity,diversity and modulability.Their simplicity is reflected in their simple composition and preparation methods used for QSFs.The diversity of supramolecular organic frameworks(SOFs) is reflected in the synthesis methods and structural characteristics of the as-obtained QSFs,as well as the variety of structural directing agents and basic building blocks used to prepare QSFs.The modulability is reflected by the controllable channel size in the QSFs,which can be adjusted using different sizes of Q[n]s.In this work,the first re ported cucurbituril Q[6]was selected as the basic building block and three Q[6]-based su p ramolecular frameworks were obtained from aqueous HCl solutions in the presence of [CdCl_(4)]^(2-)respectively.The OSIQs are the main driving forces for the formation of these frameworks.This study shows the diversity of the QSFs.
基金supported by the NSFC(Nos.21571016,21831001 and 91122028)the NSFC for Distinguished Young Scholars(No.20725101)
文摘A neoteric organic-inorganic hybrid Co-substituted phosphotungstate H6{[Co(en)2(OAc)2]2[Co4(H2 O)2(PW9 O34)2]}?2 H2 en?36 H2 O(1, en = enthylenediamine) has been made under hydrothermal conditions and characterized by IR spectrum, thermogravimetric analysis, diffuse-reflectance spectroscopy, powder X-ray diffraction, single-crystal X-ray diffraction and cyclic voltammetry, respectively. Crystal data for 1: monoclinic, P21/c, a = 18.2234(12), b = 15.3696(9), c = 20.1706(17) ?, β = 106.563(8)°, V = 5415.1(7) ?3, Z = 2, Mr = 6072.30, Dc = 3.724 g/cm3, μ = 20.087 mm-1, F(000) = 5540, R = 0.0585, w R = 0.1543 and S = 1.024. Single-crystal X-ray structure analysis reveals that compound 1 exhibits a 3-D supramolecular framework via H-bonding interactions, in which the discrete Co-complex is modified by two types of organic ligands, en and acetate. In addition, the adsorption experiments demonstrate compound 1 possesses a remarkable capability for scavenging of methylene blue.
基金supported by the Natural Science Foundation of Jiangsu Province(BK20231270)the National Science Fund for Distinguished Young Scholars(22125804).
文摘Supramolecular frameworks(SMFs)are famous for their fascinating structure and abundant porosity;however,poor crystalline stability in water severely limits their applications.Herein,an anchoringpolymerization strategy was developed under mild conditions to modulate the surface microenvironment of SMFs.The process-tracking experiment demonstrated that toluene diisocyanate(TDI)was anchored on the surface of SMF-BDC-NH_(2)before chain polymerization was initiated between TDI by introducing trace amounts of water.The glue-like polyurea armor on the surface of SMF-BDC-NH_(2)@PTDI endowed it with a water contact angle of 131.3°,and it can maintain good crystallinity and a porous structure even when immersed in water for 24 hours.SMF-BDC-NH_(2)@PTDI was proved to selectively adsorb cationic dyes,and no significant loss was detected after 5 runs,whereas the pristine material lost crystallinity and adsorption performance immediately after regeneration.The dynamic breakthrough experiment showed that SMF-BDC-NH_(2)@PTDI had an adsorption capacity of 124 mg g^(-1),positioning it among the best materials of its kind.Suitable pore size and charge interactions are proved to be the main driving forces for selective adsorption.This work may open a path to modulation of the surface microenvironment of SMFs to maintain crystalline stability and enable advanced applications in water treatment.
基金The National Natural Science Foundation of China (NSFC,Nos.92256201,52273006,22071041,92356302,and 21971052)Natural Science Foundation of Jilin Province (No.20240101181JC) are gratefully appreciated for financial the supportssupported by the User Experiment Assist System of Shanghai Synchrotron Radiation Facility (SSRF)。
文摘Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications,e.g.,encapsulating enzymes to enhance their stability,activity,and reusability.However,precise control and tune the pore size of such frameworks still remains a significant challenge to date.In this study,we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block.First,a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization.Then 2-ureido-4[1H]-pyrimidinone(Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization.Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units,well-ordered supramolecular polymer frameworks were readily obtained.Notably,the pore size was dependent on the chain length of the polyisocyanide arms.Precisely control the chain length of polyisocyanide arms,supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved.These frameworks,with tunable and large pore apertures,demonstrated exceptional capabilities in encapsulating enzymes of different sizes,such as lipase(TL),horseradish peroxidase(HRP),and glucose oxidase(GOx).The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability.Moreover,the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes,enabling efficient dual-enzyme cascade reactions.
基金the National Natural Science Foundation of China(No.21921003 for Z.T.L.and 22201293 for S.B.Y.)Shanghai Sailing Program(No.22YF1458300 for S.B.Y.)for financial support。
文摘Two supramolecular organic frameworks(SOFs)have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water.Dynamic light scattering and ^(1)H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature.One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice,which improves by 40%compared with the highest value of the reported SOFs.In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrugresistant MDR A549/ADR tumor cells to realize intracellular delivery,leading to enhanced antitumor efficacy.Moreover,it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism.As the first examples that undergo roomtemperature reversible assembly and disassembly,the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.
基金the support of National Natural Science Foundation of China(No.21601090,21761007 and 21871064)the Natural Science Foundation of Jiangsu Province(Grant No.BK20160943)+2 种基金Major Project of Basic Science(Natural Science)Research in Higher Education Institutions of Jiangsu Provincethe Basic Research Program of Shenzhen(JCYJ20190812151405298)the EPSRC for an Overseas Travel Grant.
文摘Frameworks utilizing cucurbit[n]uril-based chemistry build on the rapid developments in the fields of metal-organic frameworks(MOFs),covalent-organic frameworks(COFs)and supramolecular organic frameworks(SOFs),and as porous materials have found broad applications in heterogeneous catalysis,adsorption and ion exchange as well as other fields.Cucurbit[n]urils(Q[n]s)are suitable as the basic building blocks used for the construction of new Q[n]-based frameworks due to their special structural characteristics including the positive electrostatic potential of the outer surface,the negative portal carbonyl groups and the near neutral potential of the cavity.Herein,summaries of cucurbit[n]uril-based supramolecular frameworks assembled through outer surface interactions and cucurbit[n]uril/metal ion complex-based frameworks are discussed,and this is followed by a review of Q[n]-based frameworks assembled using the structural characteristics associated with the cavity of Q[n]s,i.e.host-vip inclusion chemistry.These assembled Q[n]-based frameworks can be catalogued as(1)simple host-vip inclusion complexes,(2)host-vip inclusion supramolecular polymers,(3)host-vip exclusion complexes or polymers and(4)coordination products of the host-vip inclusion complexes with metal ions.The design and construction of Q[n]-based frameworks via host-vip inclusion chemistry will undoubtedly enrich this new research direction in Q[n]chemistry,and will lead to multiple new applications.
基金support from the National Natural Science Foundation of China(21971257,22101060,22101302)the Hunan Provincial Science and Technology Plan Project of China(No.2019TP1001)the Excellent Youth Funding of Hunan Provincial Science and Technology Department(2022JJ20053)+2 种基金the Science and Technology Research Project of Guangzhou(202201020201,202102010432)support from the U.S.National Science Foundation(OIA-1757220)staff from the BL17B beamline of the National Facility for Protein Science Shanghai(NFPS)at the Shanghai Synchrotron Radiation Facility for their assistance during data collection.
文摘Supramolecular nanocages with inner cavities have attracted increasing attention due to their fascinating molecular aesthetics and vast number of potential applications.Even though a wide array of discrete supramolecular cages with precisely designed sizes and shapes have been established,the controlled assembly of higher-order supramolecular frameworks from discrete molecular entities still represents a formidable challenge.In this work,a novel metallo-organic cage[Zn_(12)L_(4)]was assembled based on a triphenylene-cored hexapod terpyridine ligand.Synchotron X-ray analysis revealed a pair of enantiomeric cages in the crystal with flexible ligands twisted clockwise or anticlockwise due to steric hindrance in the structure.Interestingly,due to the strongπ-πintermolecular interaction between triphenylene units,a controlled hierarchical packing of sphere-like cages in the crystal was established having a sparse packing mode with huge channels of around 3.6 nm diameter.This research sheds light on the design of strongπ-πinteractions in supramolecular hierarchical packing and materials science.
基金supported by the National Natural Science Foundation of China(21371027,20901013)the Natural Science Foundation of Liaoning Province(2015020232)the Fundamental Research Funds for the Central Universities(DUT19LK01,DUT15LN18).
文摘The selective oxidation of organic sulfides is a pivotal step in the preparation of sulfoxides that can act as synthetic intermediates when preparing fine chemicals,bioactive molecules,and asymmetric catalysis ligands.To construct high-performance heterogeneous catalysts for sulfide-sulfoxide transformations,herein,we designed and synthesized a supramolecular porous catalyst based onε-Keggin polyoxometalates(POMs),TBA_(2)H_(2)[Zn_(4)(im)(Him)_(2)][ε-PMo_(8)VMo_(4)VIO_(40)]·3H_(2)O(1,Him=1H-imidazole).Single-crystal X-ray diffraction analysis indicates that the porous framework of 1 can be obtained via the supramolecular stacking of one-dimensional helical chains alternately linked by Zn_(4)-ε-Keggin clusters and Him ligands.During the selective oxidation of methyl phenyl sulfide to methyl phenyl sulfoxide(MPSO),compound 1 achieved a>99%yield toward MPSO and 90.3%oxidant utilization efficiency within 10 min.The corresponding turnover frequency(TOF),expressing catalytic activity,was up to 1200 h^(-1).The catalyst also demonstrated extensive substrate tolerance during catalysis,and the corresponding yields of sulfoxides were satisfactory when only 1.2 equivalents of oxidant were used.Besides this,1 can also effectively degrade a sulfur mustard simulant(2-chloroethyl ethyl sulfide)to the nontoxic product 2-chloroethyl ethyl sulfoxide within 10 min at room temperature,with an oxidant utilization efficiency of up to 94.5%.Importantly,the excellent catalytic activity of compound 1 was also proven via comparison with an analogous 3D compound 2(TOF=800 h^(-1)at full MPS conversion),TBAH_(2)[K(Him)(im)][Zn_(4)(Him)(Hip)][ε-PMo_(8)VMo_(4)VIO_(40)](Hip=4-(1H-imidazol-2-yl)-pyridine),which was covalently assembled from one-dimensional Zn_(4)-ε-Keggin POM chains and metal-organic units.Moreover,the truly heterogeneous nature of 1 and 2 was confirmed via cycling and hot-filtration experiments,and their structural stability was verified based on Fourier-transform infrared spectra and powder X-ray diffractometry(PXRD)patterns.
基金supported by the National Natural Science Foundation of China(22101047,92261109,22371280)the Natural Science Foundation of Fujian Province(2023J01219)+5 种基金the Self-deployment Project Research Program of Haixi Institutes,Chinese Academy of Sciences(CXZX-2023-JQ06,CXZX-2022-JQ11)the XMIREM Autonomously Deployment Project(2023GG02,2023CX04)the FJIRSM Autonomously Deployment Project(CXZX-2022-GH02)the Project Funded by China Postdoctoral Science Foundation(2023M733496)the Recruitment Program of Global Youth Expertsthe Youth Innovation Promotion Association CAS(2021302)。
文摘Systematicly tuning the porosities of porous materials is crucial for targeted gas mixture separation,yet it remains a longstending challenge.As a common strategy,altering the phenylene ring count in the organic building units has been exploited to adjust pore apertures in metal organic frameworks(MOFs)and covalent organic frameworks(COFs),re sulting in only a stepwise pore size variation of approximately 2.8?.Unlike MOFs and COFs,the porosities for supramolecular assembly frameworks are highly dependent on the packings of the molecular building units in the lattice.The above strategy cannot be applied to supramolecular assembly frameworks and other strategies are required to adjust pore apertures in supramolecular frameworks,especially to achieve porous materials with the optimal pore size for D_(2)/H_(2)separation(~3Å).Here,we successfully modulate the poro sity of supramolecular frameworks of[Co^(Ⅱ)_(12)Co^(Ⅲ)_(8)(μ_(3)-OH)_(24)(X)]^(11+)clusters(L=mono-deprotonated 1-iminoisoindole-3-amine,X=ClO_(4)-or Cl^(-))by controlling the duration of self-assembly processes.By simply adjusting the reaction time,we obtain three[Co^(Ⅱ)_(12)Co^(Ⅲ)_(8)(μ_(3)-OH)_(24)(X)]^(11+)supramolecular frameworks:[Co_(12)^(Ⅱ)Co_(8)^(Ⅲ)(μ^(3)-OH)_(24)(ClO_(4))L_(12))]·(Cl)_(4)·(HCO_(2))_(7)(1),[Co_(12)^(Ⅱ)Co_(8)^(Ⅲ)L_(12)(μ^(3)-OH)_(24)(Cl)]·(ClO_(4))4·(Cl)_(6)·(HCO_(2))·(H_(2)O)10(2),and[Co_(12)^(Ⅱ)Co_(8)^(Ⅲ)L_(12)(μ^(3)-OH)_(24)(Cl)]·(Cl)_(11)·(H_(2)O)12(3).The different stacking patterns of the[Co^(Ⅱ)_(12)Co^(Ⅲ)_(8)(μ_(3)-OH)_(24)(X)]^(11+)clusters in these frameworks lead to significantly varied stabilities and porosities.Compound 1 exhibits permanent porosity with interconnected channels and maintains stability under harsh conditions.In contrast,compound 2 is nearly nonporous,and compound 3 becomes unstable upon desolvation.The pores of compound 1 show higher affinity to D_(2)than H_(2),and the pore aperture diameter of compound 1(~3.06Å)meets the optimal porosity for D_(2)/H_(2)separation.Consequently,compound 1 demonstrates moderate D_(2)/H_(2)separation at 77 K(retention time:~7 min/g for D_(2)/H_(2)/Ne(10/10/80 vol%)in a flow of 5 mL/min).These results provide a new strategy to tune the porosities of porous supramolecular materials for target gas mixture separation.
基金Supported by the National Natural Science Foundation of China(Grant No.20671071)Program for New Century Excellent Talents in University(Grant No.NCET-07-0613),and Tianjin Normal University
文摘A series of Cd(Ⅱ)coordination complexes with an elongated 2,4-dipyridyl-type building block trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene(bpe)and different dicarboxylate ligands have been presented.Generally,bpe shows the unidentate coordination mode and serves as the terminal pendant,whereas the dicarboxylate ligands display various binding fashions to interlink the metal centers to form 1-D comb-like chain,ribbon,and fishbone arrays,as well as 2-D 44 and 4.82 layered networks.Notably,the bpe building block is also involved in secondary interactions such as hydrogen bonding and aromatic stacking to construct the resulting supramolecular architectures.Thermal stability of these complexes has been studied by TG-DTA technique.
基金This study was financially supported by the National Nature Science Foundation of China(nos.21771177 and 51603206)the Strategic Priority Research Program of CAS(no.XDB20000000)the Key Research Program of Frontier Sciences,CAS(no.QYZDB-SSW-SLH019).
文摘Porous supramolecular frameworks based on metal-organic cages(MOCs)usually have poor structural stability after activation.This issue narrows the scope of their potential applications,particularly for the inclusion of vip molecules that demand high porosity.Herein,the authors have reported the stabilization of a mesoporous zirconium MOC-based supramolecular framework with an in situ catalytic polymerization strategy.Due to the passivation effect imparted by this strategy,the introduced polymer is primarily distributed on the surface of the crystals,which results in the hybrid material retaining its crystallinity and permanent porosity.A preliminary application of this type of stabilized mesoporous supramolecular framework shows that among MOC-based supramolecular frameworks,it has the highest high-pressure methane uptake.Such a facile strategy may provide a general way to stabilize fragile porous materials and facilitate exploration of their potential applications.
基金support from the National Key Research and Development Program of China(No.2017YFA0700102)the National Natural Science Foundation of China(Nos.21871266 and 21731006)+1 种基金the Key Research Program of Frontier Science CAS(No.QYZDY-SSW-SLH025)Youth Innovation Promotion Association CAS.
文摘A microporous supramolecular framework with high water and thermal stability can selectively absorb water molecules over methanol or ethanol due to the suitable channels.The model separation test on columns shows that an ultra-pure ethanol(99.9%)can be obtained from the mixture of ethanol/water(95:5).Additionally,after refluxing the desolvated sample in 95%ethanol at 60℃for 5 h,the purity of ethanol rises up to 97.43%,which is obviously higher than 96.56%for 4 A molecular sieves.
基金supported by the National Natural Science Foundation of China(Nos.21971091,21901089 and 22161021)the Natural Science Foundation of Jiangxi Province(No.20212BAB203021)
文摘Accompanied by solid-state structural phase transitions,the switchable molecular dynamics(MD)and order-disorder transformation of(i-PrNHMe2)^(+)cation embedded in a deformable{[Ni(NCS)_(6)]^(4-)}_(∞)supramolecular framework are in-depth investigated by variable-temperature tests of single-crystal X-ray diffraction,dielectric measurement,and MD simulation.Interestingly,it is found that the confined swinging or flipping of the(i-PrNHMe_(2))^(+)cation as a whole is assisted by a synergistic change of its torsion angle.This research provides a helpful insight into the solid-state MD of moderate-sized quasi-spherical molecules/ions that feature a flexible inner core.
基金financially supported by the National Natural Science Foundation of China (Nos. 21472225, 21725404)the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDAB20000000)
文摘Two-dimensional(2D) materials have been demonstrated to exhibit unique properties originating from its 2D nature. In recent years, the construction of 2D materials has become a topic of great interest. This article summarizes the recent advance of 2D supramolecular organic frameworks(SOFs) which are homogeneously constructed in solution phase through self-assembly of rationally designed building blocks. These 2D SOFs are soluble and still maintain stable network structures in solutions, which exhibit uniqueness not only in structures but also in properties. In this concise review, the SOFs-related background is briefly introduced firstly, followed by outlining the research progress of soluble 2D SOFs from the perspective of monomer design, assembly, and structural characterization.The article ends with a personal outlook on the future development of this new class of supramolecular polymers.
基金supported by the National Natural Science Foundation of China (Nos. 21432004 and 21890732)
文摘Ru(bpy)3]2+-cored supramolecular organic framework SMOF-1, assembled from a [Ru(bpy)3]2+-derived hexaarmed molecule and cucurbit[8]uril, has been demonstrated to heterogeneously catalyze visible light-induced reduction of phenyl, benzyl, 2-phenylethyl and 3-phenylpropyl azides in acetonitrile to produce the corresponding amines in good to high yields. For the last two kinds of azides that bear a CO2Me group at the para-position of the benzene ring, cascade reactions take place to generate the corresponding lactams in high yields. Compared with homogeneous control [Ru(bpy)3]Cl2, SMOF-1 exhibits remarkably increased photocatalysis activity as a result of synergistic effect of the [Ru(bpy)3]2+ units that form cubic cages to host the azide molecules and related intermediates. Moreover, SMOF-1 displays high recyclability and considerable photocatalysis activity after 3 to 12 runs.
基金the National Natural Science Foundation of China (Nos.21432004,21529201,91527301)the Ministry of Science and Technology of China(No.2013CB834501)+1 种基金the Ministry of Education of China Research Fund for the Doctoral Program and of China for financial supportsupport from the Molecular Foundry,Lawrence Berkeley National Laboratory,supported by the Office of Science,Office of Basic Energy Sciences,Scientific User Facilities Division,of the U.S.Department of Energy under Contract No.DE-AC0205CH11231
文摘Four water-soluble porous supramolecular organic framework drug delivery systems（sof-DDSs） have been used to adsorb doxorubicin（DOX） in water at physiological pH of 7.4,which is driven exclusively by hydrophobicity.The resulting complexes DOX@SOFs are formed instantaneously upon dissolving the components in water.The drug-adsorbed sof-DDSs can undergo plasm circulation with important maintenance of the drug and overcome the multidrug resistance of human breast MCF-7/Adr cancer cells.DOX is released readily in the cancer cells due to the protonation of its amino group in the acidic medium of cancer cells.In vitro and in vivo experiments reveal that the delivery of SOF-a-d remarkably improve the cytotoxicity of DOX for the MCF-7/Adr cells and tumors,leading to 13-19-fold reduction of the 1C_（50）values as compared with that of DOX.This new sof-DDSs strategy omits the indispensable loading process required by most of reported nano-scaled carriers for neutral hydrophobic chemotherapeutic agents,and thus should be highly valuable for future development of low-cost delivery systems.
基金the National Natural Science Foundation of China(Nos.21432004,21529201,and 91527301)the Ministry of Science and Technology of China(No.2013CB834501)+1 种基金the Ministry of Education of China Research Fund for the Doctoral Program and of China for financial supportsupport from the Molecular Foundry,Lawrence Berkeley National Laboratory,supported by the Office of Science,Office of Basic Energy Sciences,Scientific User Facilities Division,of the U.S.Department of Energy under Contract No.DE-AC02-05CH11231
文摘Water-soluble three-dimensional porous supramolecular organic frameworks（SOFs） have been demonstrated as a new generation of homogeneous polycationic platforms for anti-cancer drug delivery.The new SOF drug delivery systems（sof-DDSs） can adsorb dianionic pemetrexed（PMX）,a clinically used chemotherapeutic agent instantaneously upon dissolving in water,which is driven by both electrostatic attraction and hydrophobicity.The in situ-prepared PMX@SOFs are highly stable and can avoid important release of the drug during plasm circulation and overcome the multidrug resistance of human breast MCF-7/Adr cancer cells to enter the cancer cells.Acidic microenvironment of cancer cells promotes the release of the drug in cancer cells.Both in vitro and in vivo studies have revealed that sofDDSs considerably improve the treatment efficacy of PMX,leading to 6-12-fold reduction of the IC50 values,as compared with that of PMX alone.The new drug delivery strategy omits the loading process required by most of reported nanoparticle-based delivery systems and thus holds promise for future development of low-cost drug delivery systems
基金supports from the National Natural Science Foundation of China(Nos.21890732,21890730 and 21921003)。
文摘Here we use nor-seco-cucurbit[10]uril(ns-CB[10]) based ternary complexation to construct [5]rotaxane,linear supramolecular dynamic rotaxane polymers and cubic 3D supramolecular organic framework.A [5]rotaxane is constructed by ns-CB[10], TMe CB[6] and short linear derivatives of 4,4'-bipyridinium(M2). ns-CB[10], CB[7] and long linear derivatives of 4,4'-bipyridinium(M3) self-assemble into a linear supramolecular dynamic rotaxane polymer. ns-CB[10] and tetracationic tetrahedral monomer selfassemble and form a three-dimensional supramolecular organic framework. The above results demonstrate that ns-CB[10]-based ternary complexation is a versatile platform to build various supramolecular systems.
