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1.
DNA‐based shape‐memory hydrogels revealing switchable shape recovery in the presence of two orthogonal triggers are described. In one system, a shaped DNA/acrylamide hydrogel is stabilized by duplex nucleic acids and pH‐responsive cytosine‐rich, i‐motif, bridges. Separation of the i‐motif bridges at pH 7.4 transforms the hydrogel into a quasi‐liquid, shapeless state, that includes the duplex bridges as permanent shape‐memory elements. Subjecting the quasi‐liquid state to pH 5.0 or Ag+ ions recovers the hydrogel shape, due to the stabilization of the hydrogel by i‐motif or C‐Ag+‐C bridged i‐motif. The cysteamine‐induced transformation of the duplex/C‐Ag+‐C bridged i‐motif hydrogel into a quasi‐liquid shapeless state results in the recovery of the shaped hydrogel in the presence of H+ or Ag+ ions as triggers. In a second system, a shaped DNA/acrylamide hydrogel is generated by DNA duplexes and bridging Pb2+ or Sr2+ ions‐stabilized G‐quadruplex subunits. Subjecting the shaped hydrogel to the DOTA or KP ligands eliminates the Pb2+ or Sr2+ ions from the respective hydrogels, leading to shapeless, memory‐containing, quasi‐liquid states that restore the original shapes with Pb2+ or Sr2+ ions.  相似文献   

2.
Synthesis and Reactivity of 2‐Bromo‐1,3‐diethyl‐2,3‐dihydro‐1 H ‐1,3,2‐benzodiazaborole Molecular Structure of Bis(1,3‐diethyl‐2,3‐dihydro‐1 H ‐1,3,2‐benzodiazaborol‐2‐yl The reaction of a slurry of calcium hydride in toluene with N,N′‐diethyl‐o‐phenylenediamine ( 1 ) and boron tribromide affords 2‐bromo‐1,3‐diethyl‐2,3‐dihydro‐1 H‐1,3,2‐benzodiazaborol ( 2 ) as a colorless oil. Compound 2 is converted into 2‐cyano‐1,3‐diethyl‐2,3‐dihydro‐1 H‐1,3,2‐benzodiazaborole ( 3 ) by treatment with silver cyanide in acetonitrile. Reaction of 2 with an equimolar amount of methyllithium affords 1,3‐diethyl‐2‐methyl‐2,3‐dihydro‐1 H‐1,3,2‐benzodiazaborole ( 4 ). 1,3,2‐Benzodiazaborole is smoothly reduced by a potassium‐sodium alloy to yield bis(1,3‐diethyl‐2,3‐dihydro‐1 H‐1,3,2‐benzodiazaborol‐2‐yl] ( 7 ), which crystallizes from n‐pentane as colorless needles. Compound 7 is also obtained from the reaction of 2 and LiSnMe3 instead of the expected 2‐trimethylstannyl‐1,3,2‐benzodiazaborole. N,N′‐Bis(1,3‐diethyl‐2,3‐dihydro‐1 H‐1,3,2‐benzodiazaborol‐2‐ yl)‐1,2‐diamino‐ethane ( 6 ) results from the reaction of 2 with Li(en)C≡CH as the only boron containing product. Compounds 2 – 4 , 6 and 7 are characterized by means of elemental analyses and spectroscopy (IR, 1H‐, 11B{1H}‐, 13C{1H}‐NMR, MS). The molecular structure of 7 was elucidated by X‐ray diffraction analysis.  相似文献   

3.
The crystal structure of the title compound, [CoCl(C18H37N4O2){ZnCl3}], has been determined by X‐ray diffraction.Cmeso‐5,5,7,12,12,14‐Hexa­methyl‐1,4,8,11‐tetra­aza­cyclotetradecane‐N‐acetate acts as a bridging ligand to coodinate with CoIII and ZnII ions. The CoIII ion is six‐coordinate in a nearly octahedral environment provided by one Cl atom, four N atoms of the bridging ligand, and one O atom. The ZnII ion is four‐coordinate in a distorted tetrahedral environment completed by three Cl atoms and an O atom of the bridging ligand.  相似文献   

4.
The 1‐cyclopropyl‐6‐fluoro‐1,4‐dihydro‐4‐oxo‐7‐(piperazin‐1‐yl)quinoline‐3‐carboxylic acid (=ciprofloxacin; 1 ) undergoes low‐efficiency (Φ=0.07) substitution of the 6‐fluoro by an OH group on irradiation in H2O via the ππ* triplet (detected by flash photolysis, λmax 610 nm, τ 1.5 μs). Decarboxylation is a minor process (≤5%). The addition of sodium sulfite or phosphate changes the course of the reaction under neutral conditions. Reductive defluorination is the main process in the first case, while defluorination is accompanied by degradation of the piperazine moiety in the presence of phosphate. In both cases, the initial step is electron‐transfer quenching of the triplet (kq=2.3⋅108M −1 s−1 and 2.2⋅107M −1 s−1, respectively). Oxoquinoline derivative 1 is much more photostable under acidic conditions, and in this case the F‐atom is conserved, and the piperazine group is stepwise degraded (Φ=0.001).  相似文献   

5.
Octafluoro‐1, 2‐dimethylenecyclobutane, a Perfluorinated Diene Ligand — Carbonyl(η5‐cyclopentadienyl)(η4‐octafluoro‐1, 2‐dimethylenecyclobutane)manganese The [2+2]‐cycloaddition product of tetrafluoroallene ( 1 ), octafluoro‐1, 2‐dimethylenecyclobutane ( 2 ) reacts with tricarbonyl(η5‐cyclopentadienyl)manganese ( 4 ) replacing two carbonyl ligands to give carbonyl(η5‐cyclopentadienyl)(η4‐octafluoro‐1, 2‐dimethylenecyclobutane)manganese ( 5 ). According to the IR spectrum of 5 , the ligand 2 is a strong π acceptor. Among the less volatile by‐products of the dimerizationof 1 , the hydrolysis product of its trimer could be structurally characterized by X‐ray diffraction as the spirocyclic compound decafluoro‐5‐methylene‐spiro[3.3]heptane‐2‐carboxylic acid ( 3 ). The structure of 5 was also determined by an X‐ray crystal structure determination.  相似文献   

6.
In the title coordination polymer, [Ba(1,3‐BDOA)(H2O)2]n (where 1,3‐BDOA2− is the m‐phenylenedioxydiacetate dianion, C10H8O6), each BaII ion is ten‐coordinated by six carboxyl O atoms and two ether O atoms from different 1,3‐BDOA2− ligands, as well as by two water mol­ecules, thus defining a dodeca­hedron. The BaII atoms are covalently linked by 1,3‐BDOA2− ligands in different crystallographic directions, giving rise to a three‐dimensional open framework. The crystal structure is further stabilized by hydrogen bonds and π–π stacking inter­actions. In previously studied polymers of this type, the 1,3‐BDOA2− ligand showed multiple bridging modes with metal ions, including bi‐, tri‐, tetra‐ and hexa­dentate. The title BaII complex represents a novel three‐dimensional coordination polymer constructed by octa­dentate bridging 1,3‐BDOA2− ligands.  相似文献   

7.
In the title three‐dimensional coordination polymer, [Sr(4‐CPOA)(H2O)]n (where 4‐CPOA2− is the 4‐carboxylatophenoxy­acetate dianion, C9H6O5), each SrII atom displays a bicapped triangular prismatic configuration, defined by five carboxyl and one ether O atom from five different 4‐CPOA2− ligands, as well as two water mol­ecules. The SrII atoms are covalently linked by 4‐CPOA2− ligands and water mol­ecules, giving rise to a three‐dimensional open framework. In previously studied polymers of this type, the 4‐CPOA2− ligand shows a variety of binding modes to metal ions, from mono‐ to pentadentate. In the present SrII complex, a novel hexadentate bridging mode is observed.  相似文献   

8.
An efficient functional mimic of the photosynthetic antenna‐reaction center has been designed and synthesized. The model contains a near‐infrared‐absorbing aza‐boron‐dipyrromethene (ADP) that is connected to a monostyryl boron‐dipyrromethene (BDP) by a click reaction and to a fullerene (C60) using the Prato reaction. The intramolecular photoinduced energy and electron‐transfer processes of this triad as well as the corresponding dyads BDP‐ADP and ADP‐C60 have been studied with steady‐state and time‐resolved absorption and fluorescence spectroscopic methods in benzonitrile. Upon excitation, the BDP moiety of the triad is significantly quenched due to energy transfer to the ADP core, which subsequently transfers an electron to the fullerene unit. Cyclic and differential pulse voltammetric studies have revealed the redox states of the components, which allow estimation of the energies of the charge‐separated states. Such calculations show that electron transfer from the singlet excited ADP (1ADP*) to C60 yielding ADP.+‐C60.? is energetically favorable. By using femtosecond laser flash photolysis, concrete evidence has been obtained for the occurrence of energy transfer from 1BDP* to ADP in the dyad BDP‐ADP and electron transfer from 1ADP* to C60 in the dyad ADP‐C60. Sequential energy and electron transfer have also been clearly observed in the triad BDP‐ADP‐C60. By monitoring the rise of ADP emission, it has been found that the rate of energy transfer is fast (≈1011 s?1). The dynamics of electron transfer through 1ADP* has also been studied by monitoring the formation of C60 radical anion at 1000 nm. A fast charge‐separation process from 1ADP* to C60 has been detected, which gives the relatively long‐lived BDP‐ADP.+C60.? with a lifetime of 1.47 ns. As shown by nanosecond transient absorption measurements, the charge‐separated state decays slowly to populate mainly the triplet state of ADP before returning to the ground state. These findings show that the dyads BDP‐ADP and ADP‐C60, and the triad BDP‐ADP‐C60 are interesting artificial analogues that can mimic the antenna and reaction center of the natural photosynthetic systems.  相似文献   

9.
A porous crystal family has been explored as alternatives of Nafion films exhibiting super‐proton conductivities of ≥10−2 S cm−1. Here, the proton‐conduction natures of a solution‐processed film of nanoparticles (NPs) have been studied and compared to those of a Nafion film. A mono‐particle film of Prussian‐blue NPs is spontaneously formed on a self‐assembled monolayer substrate by a one‐step solution process. A low‐temperature heating process of the densely packed, pinhole‐free mono‐particle NP film enables a maximum 105‐fold enhancement of proton conductivity, reaching ca. 10−1 S cm−1. The apparent highest conductivity, compared to previously reported data of the porous crystal family, remains constant against humidity changes by an improved water‐retention ability of the film. In our proposed mechanism, the high‐performing solution‐processed NP film suggests that heating leads to the self‐restoration of hydrogen‐bonding networks throughout their innumerable grain boundaries.  相似文献   

10.
In the title two‐dimensional coordination polymer, [Mn(1,4‐BDOA)(4,4‐bipy)(H2O)2]n [1,4‐BDOA2− is the p‐phenyl­ene­dioxy­di­acetate dianion (C10H8O6) and 4,4‐bipy is 4,4‐bi­pyridine (C10H8N2)], each MnII atom displays octahedral coordination by two O atoms of the 1,4‐BDOA2− groups, two N atoms of the 4,4‐bipy ligands and two solvent water mol­ecules. The MnII atom, 4,4‐bipy ligand and 1,4‐BDOA2− group occupy different inversion centres. Adjacent MnII atoms are bridged by 1,4‐BDOA2− groups and 4,4‐bipy ligands, forming a two‐dimensional network with Mn⋯Mn separations of 11.592 (2) and 11.699 (2) Å. Hydro­gen bonds from a water O—H group link the layers in the third dimension.  相似文献   

11.
One of most interesting systems of coordination polymers constructed from the first‐row transition metals is the porous ZnII coordination polymer system, but the numbers of such polymers containing N‐donor linkers are still limited. The title double‐chain‐like ZnII coordination polymer, [Ag2Zn(CN)4(C10H10N2)2]n, presents a one‐dimensional linear coordination polymer structure in which ZnII ions are linked by bridging anionic dicyanidoargentate(I) units along the crystallographic b axis and each ZnII ion is additionally coordinated by a terminal dicyanidoargentate(I) unit and two terminal 1‐benzyl‐1H‐imidazole (BZI) ligands, giving a five‐coordinated ZnII ion. Interestingly, there are strong intermolecular AgI…AgI interactions between terminal and bridging dicyanidoargentate(I) units and C—H…π interactions between the phenyl rings of BZI ligands of adjacent one‐dimensional linear chains, providing a one‐dimensional linear double‐chain‐like structure. The supramolecular three‐dimensional framework is stabilized by C—H…π interactions between the phenyl rings of BZI ligands and by AgI…AgI interactions between adjacent double chains. The photoluminescence properties have been studied.  相似文献   

12.
A Cyclic Methylenediphosphinic Acid: 1,3‐Dihydroxy‐1,3‐dioxo‐1,2,3,4‐tetrahydro‐1λ5,3λ5‐[1,3]diphosphinine Strong acids protonate 1,3‐bis(dimethylamino)‐1λ5,3λ5‐[1,3]diphosphinine ( 5 ) to give the corresponding cation. The protonation is followed by hydrolytic cleavage of the dimethylamino groups resulting in the formation of the cyclic methylenediphosphinic acid ( 6 ).  相似文献   

13.
In recent years, coordination polymers constructed from multidentate carboxylate and pyridyl ligands have attracted much attention because these ligands can adopt a rich variety of coordination modes and thus lead to the formation of crystalline products with intriguing structures and interesting properties. A new coordination polymer, namely poly[[μ2‐1,6‐bis(pyridin‐3‐yl)‐1,3,5‐hexatriene‐κ2N:N′](μ3‐naphthalene‐1,4‐dicarboxylato‐κ4O1,O1′:O4:O4′)zinc(II)], [Zn(C12H6O4)(C16H14N2)]n, has been prepared by the self‐assembly of Zn(NO3)2·6H2O, naphthalene‐1,4‐dicarboxylic acid (1,4‐H2ndc) and 1,6‐bis(pyridin‐3‐yl)‐1,3,5‐hexatriene (3,3′‐bphte) under hydrothermal conditions. The title compound has been structurally characterized by IR spectroscopy, elemental analysis, powder X‐ray diffraction and single‐crystal X‐ray diffraction analysis. Each ZnII ion is six‐coordinated by four O atoms from three 1,4‐ndc2− ligands and by two N atoms from two 3,3′‐bphte ligands, forming a distorted octahedral ZnO4N2 coordination geometry. Pairs of ZnII ions are linked by 1,4‐ndc2− ligands, leading to the formation of a two‐dimensional square lattice ( sql ) layer extending in the ab plane. In the crystal, adjacent layers are further connected by 3,3′‐bphte bridges, generating a three‐dimensional architecture. From a topological viewpoint, if each dinuclear zinc unit is considered as a 6‐connected node and the 1,4‐ndc2− and 3,3′‐bphte ligands are regarded as linkers, the structure can be simplified as a unique three‐dimensional 6‐connected framework with the point symbol 446108. The thermal stability and solid‐state photoluminescence properties have also been investigated.  相似文献   

14.
The title compound, μ‐aqua‐1:2κ2O‐penta­aqua‐1κ2O,2κ3O‐μ‐3,6‐bis(6‐methyl‐2‐pyridyl)­pyridazine‐1κ2N1,N6:2κ2N2,N3‐chloro‐1κCl‐dinickel(II) trichloride trihydrate, [Ni2Cl(C16H14­N4)(H2O)6]Cl3·3H2O, consists of two NiII atoms, a 3,6‐bis(6‐methyl‐2‐pyridyl)­pyridazine mol­ecule, four Cl atoms and nine water mol­ecules. The two Ni atoms are octahedrally coordinated by N and Cl atoms, and by water mol­ecules, and the three six‐membered rings, a pyridazine and two picolines, are planar to within 0.181 (3) Å. The crystal structure is stabilized by an intra‐ and intermolecular hydrogen‐bonding scheme involving water–water and water–chlorine interactions.  相似文献   

15.
In positron emission tomography (PET), which exploits the affinity of a radiopharmaceutical for the target organ, a systematic repertoire of oxygen‐15‐labeled PET tracers is expected to be useful for bioimaging owing to the ubiquity of oxygen atoms in organic compounds. However, because of the 2‐min half‐life of 15O, the synthesis of complex biologically active 15O‐labeled organic molecules has not yet been achieved. A state‐of‐the‐art synthesis now makes available an 15O‐labeled complex organic molecule, 6‐[15O]‐2‐deoxy‐D ‐glucose. Ultrarapid radical hydroxylation of 2,6‐dideoxy‐6‐iodo‐D ‐glucose with molecular oxygen labeled with 15O of two‐minute half‐life provided the target 15O‐labeled molecule. The labeling reaction with 15O was complete in 1.3 min, and the entire operation time starting from the generation of 15O‐containing dioxygen by a cyclotron to the purification of the labeled sugar was 7 min. The labeled sugar accumulated in the metabolically active organs as well as in the bladder of mice and rats. 15O‐labeling offers the possibility of repetitive scanning and the use of multiple PET tracers in the same body within a short time, and hence should significantly expand the scope of PET studies of small animals.  相似文献   

16.
The crystal structure of the title potassium salt, K+·C8HN4O2, of the organic anion 3‐cyano‐4‐(di­cyano­methyl­ene)‐5‐oxo‐4,5‐di­hydro‐1H‐pyrrol‐2‐olate shows that the di­cyano­methyl­ene moiety is able to accept an electron in the same way as does tetra­cyano­ethyl­ene, to yield the novel product. The organic anion is nearly planar, with deviations caused by steric crowding among the exocyclic cyano groups. The K+ cations lie within tricapped trigonal prisms that stack to form channels. The three‐dimensional structure is completed by the formation of hydrogen‐bonded chains by the anions.  相似文献   

17.
The title compound, [Pb(C12H7N2O4)2]n, obtained by reaction of Pb(NO3)2 and 2,2′‐bipyridine‐5,5′‐dicarboxylic acid (H2bptc) under hydrothermal conditions, has a structure in which the unique PbII cation sits on a twofold axis and is octa‐coordinated by four O‐atom donors from four Hbptc ligands and four N‐atom donors from two Hbptc ligands in a distorted dodecahedral geometry. With each PbII cation connected to six Hbptc ligands and each Hbptc ligand bridging three PbII cations, a three‐dimensional polymeric structure is formed. From a topological point of view, the three‐dimensional net is binodal, with six‐connected (the PbII cation) and three‐connected (the Hbptc ligand) nodes, resulting in a distorted rutile (42.8)2(4489122) topology.  相似文献   

18.
All‐DNA scaffolds act as templates for the organization of photosystem I model systems. A series of DNA templates composed of ZnII‐protoporphyrin IX (ZnIIPPIX)‐functionalized G‐quadruplex conjugated to the 3′‐ or 5′‐end of the tyrosinamide (TA) aptamer and ZnIIPPIX/G‐quadruplex linked to the 3′‐ and 5′‐ends of the TA aptamer through a four‐thymidine bridge. Effective photoinduced electron transfer (ET) from ZnIIPPIX/G‐quadruplex to bipyridinium‐functionalized tyrosinamide, TA‐MV2+, bound to the TA aptamer units is demonstrated. The effectiveness of the primary ET quenching of ZnIIPPIX/G‐quadruplex by TA‐MV2+ controls the efficiency of the generation of TA‐MV+.. The photosystem‐controlled formation of TA‐MV+. by the different photosystems dictates the secondary activation of the ET cascade corresponding to the ferredoxin‐NADP+ reductase (FNR)‐catalysed reduction of NADP+ to NADPH by TA‐MV+., and the sequestered alcohol dehydrogenase catalysed reduction of acetophenone to 1‐phenylethanol by NADPH.  相似文献   

19.
Three Ru–η6‐benzene–phosphine complexes bearing tri‐(p‐methoxyphenyl)phosphine, triphenylphosphine and tri‐(p‐trifluoromethylphenyl)phosphine were synthesized and characterized by 31P{1H} NMR, 1H NMR, 13C{1H} NMR and elemental analyses. Complex 1 was further identified by X‐ray crystallography. These complexes exhibit good to excellent activities for the transfer hydrogenation of ketones in refluxing 2‐propanol, and the highest turnover frequency (TOF) is up to 5940 h−1. The effect of electronic factors of these complexes on the transfer hydrogenation of ketones reveals that the catalytic activity is promoted by electron‐donating phosphine and the catalyst stability is improved by electron‐withdrawing phosphine. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

20.
The bifunctional pyridine‐2,3‐dicarboxylic acid (H2pdc) ligand has one N atom and four O atoms, which could bind more than one AgI centre with diverse binding modes. A novel infinite one‐dimensional AgI coordination polymer, namely catena‐poly[[silver(I)‐(μ2‐pyridine‐2,3‐dicarboxylato‐κ2N :O 3)‐silver(I)‐tris(μ2‐5‐methyl‐1,3,4‐thiodiazol‐2‐amine‐κ2N :N ′)] monohydrate ethanol monosolvate], {[Ag2(C7H3NO4)(C3H5N3S)3]·H2O·C2H5OH}n , has been synthesized using H2pdc and 5‐methyl‐1,3,4‐thiadiazol‐2‐amine (tda), and characterized by single‐crystal X‐ray diffraction. One AgI atom is located in a four‐coordinated AgN4 tetrahedral geometry and the other AgI atom is in a tetrahedral AgN3O geometry. A dinuclear AgI cluster formed by three tda ligands with a paddelwheel configuration is bridged by the dianionic pdc2− ligand into a one‐dimensional coordination polymer. Interchain N—H…O hydrogen bonds extend the one‐dimensional chains into an undulating two‐dimensional sheet. The sheets are further packed into a three‐dimensional supramolecular framework by interchain N—H…O hydrogen bonds.  相似文献   

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