Self-assembly and molecular recognition of adenine- and thymine-functionalized nucleolipids in the mixed monolayers and thymine-functionalized nucleolipids on aqueous melamine at the air-water interface

Self-assembly and molecular recognition of the monolayers composed of an equimolar mixture of adenine- and thymine-functionalized nucleolipids at the air-water interface have been investigated in detail using surface pressure-molecular area isotherms and in situ infrared reflection absorption spectroscopy (IRRAS). Prior to molecular recognition, the adenine moieties in the monolayer were almost oriented on an end-on mode through π-stacking and hydrogen bonding interactions, and the C-C-C planes of the alkyl chains were preferentially oriented perpendicular to the water surface, while the thymine moieties in the monolayer were involved in hydrogen bonding almost with a flat-on orientation. On aqueous subphases containing complementary bases, no significant molecular recognition was observed for the monolayers of individual nucleolipids. In the monolayer of equimolar mixture, molecular recognition occurred between the adenine and thymine moieties through hydrogen bonding probably with the development of cyclic structures of adenine-thymine-adenine-thymine quartets. Although molecular recognition between the monolayer of thymine-functionalized nucleolipids and aqueous melamine took place through triple hydrogen bonds, no melamine binding to the monolayer of equimolar mixture was observed, which reflects the formation of the quartets in the mixed monolayers at the air-water interface. FTIR and small-angle X-ray diffraction (XRD) results of the corresponding Langmuir-Blodgett films support the hydrogen bonding recognition and molecular orientation.     

Specific interactions of complementary mono- and multivalent guests with recognition-induced polymersomes

We have explored the interactions of mono- and multivalent guests with Recognition-Induced Polymersomes (RIPs) formed from complementary random copolymers featuring diamidopyridine and thymine functionality. Addition of monovalent guests featuring imide functionality to these RIPs induced a temporary swelling of the vesicles, followed by dissociation of the vesicles due to competitive binding of the guest. Conversely, multivalent thymine-functionalized nanoparticle guests were rapidly incorporated into the RIPs, inducing a contraction of RIP diameter over time. These mono- and multivalent interactions were extremely specific: highly analogous control systems showed no interaction with the RIP structures. Taken together, these studies demonstrate highly selective molecular "lock and key" control over higher-order assembly and recognition processes.     

Recognition-induced transformation of microspheres into vesicles: morphology and size control

Polystyrene functionalized with diamidopyridine (DAP) recognition units self-assembles in nonpolar media to form thermally reversible micrometer-scale spherical aggregates. The size and the thermal stability of these microspheres can be controlled by the molecular weight of the polymer. The addition of thymine-functionalized polymer to these self-assembled microspheres converted them into vesicular aggregates with a controlled size. The morphology change was reversible: the addition of DAP-functionalized polymer converted the vesicles back to microspheres.     

Self-assembly of gold nanoparticles through tandem hydrogen bonding and polyoligosilsequioxane (POSS)-POSS recognition processes

Diaminopyridine-functionalized polyhedral oligomeric silsequioxanes (POSS-DAP) self-assemble with complementary thymine-functionalized Au nanoparticles (Thy-Au) into well-defined spherical aggregates, providing highly structured nanocomposites.     

Core-bound polymeric micellar system based on photocrosslinking of thymine

Bioinspired core-bound polymer micellar aggregates were synthesized by photocrosslinking thymine-functionalized cores using short UV irradiation; H-bonding between thymines in the core is also believed to increase micellar aggregate stability.     

Template-assisted preferential formation of a syn photodimer in a pyrophosphate-induced self-assembly of a thymine-functionalized isothiouronium receptor

[reaction: see text] The effect of anion templation is investigated for the photodimerization of a thymine-functionalized isothiouronium receptor. The receptor forms a photodimer at the thymine moiety in methanol upon UV irradiation, while the isothiouronium moiety works as an oxoanion binding site via a two-point hydrogen-bonding motif. As compared to the case of a free receptor, the presence of pyrophosphate (PPi) resulted in the preferential formation of the syn-type photodimer, which would be desirable for recognizing the templated PPi.     

Multiple hydrogen bonding for reversible polymer surface adhesion

Specific and reversible adhesion of a terminal thymine-functionalized polystyrene (PS-thymine) was demonstrated for a silicon surface with complementary adenine recognition sites. A novel adenine-containing triethoxysilane (ADPTES), which was suitable for covalent attachment to silanol containing surfaces, was synthesized in one step from adenine and 3-isocyanatopropyl triethoxysilane (IPTES). 1H and 13C NMR spectroscopy and fast atom bombardment mass spectroscopy confirmed the chemical structure, and 29Si NMR spectroscopy indicated the absence of any premature hydrolysis of the alkoxysilane derivative. X-ray photoelectron spectroscopy (XPS) and water contact angle measurements indicated the attachment of PS-thymine to silicon surfaces that were modified with a mixture of ADPTES and 3-mercaptopropyl triethoxysilane (MPTES). PS-thymine attachment to surfaces that were modified with only MPTES was not observed. The exclusive attachment of PS-thymine to an ADPTES/MPTES-modified surface confirmed hydrogen bonding-mediated adenine-thymine association to silicon surfaces containing a sufficiently low concentration of adenine recognition sites. Although PS-thymine attachment to the ADPTES/MPTES-modified surfaces was insensitive to THF rinsing, the PS-thymine was completely removed from the surface upon DMSO rinsing because of the disruption of adenine-thymine hydrogen bonding with a more polar aprotic solvent. PS-thymine was successfully reattached to the ADPTES/MPTES-modified surface following the DMSO rinse, demonstrating the solvato-reversible nature of the adenine-thymine association.     

A light-responsive reversible molecule-gated system using thymine-modified mesoporous silica nanoparticles

In this paper, a reversible light-responsive molecule-gated system based on mesoporous silica nanoparticles (MSN) functionalized with thymine derivatives is designed and demonstrated. The closing/opening protocol and release of the entrapped guest molecules is related by a photodimerization-cleavage cycle of thymine upon different irradiation. In the system, thymine derivatives with hydrophilicity and biocompatibility were grafted on the pore outlets of MSN. The irradiation with 365 nm wavelength UV light to thymine-functionalized MSN led to the formation of cyclobutane dimer in the pore outlet, subsequently resulting in blockage of pores and strongly inhibiting the diffusion of guest molecules from pores. With 240 nm wavelength UV light irradiation, the photocleavage of cyclobutane dimer opened the pore and allowed the release of the entrapped guest molecules. As a proof-of-the-concept, Ru(bipy)(3)(2+) was selected as the guest molecule. Then the light-responsive loading and release of Ru(bipy)(3)(2+) were investigated. The results indicated that the system had an excellent loading amount (53 μmol g(-1) MSN) and controlled release behavior (82% release after irradiation for 24 h), and the light-responsive loading and release procedure exhibited a good reversibility. Besides, the light-responsive system loaded with Ru(bipy)(3)(2+) molecule could also be used as a light-switchable oxygen sensor.     

Structure and properties of composites of highly crystalline cellulose with polypropylene: Effects of polypropylene molecular weight

Composite of highly crystalline fibrous cellulose (CE) and polypropylene (PP) of different molecular weights () was prepared via melting-mixing, maleic anhydride grafted polypropylene (MAPP) was used as a compatibilizer. And the effects of molecular weight of PP on the properties of the composites were investigated. Through the studying of mechanical properties, dynamic mechanical properties, melting and crystallization behaviors, thermo-oxidative properties, water absorption behaviors, and the morphology of the composites, it was found that PP with higher molecular weight revealed stronger interfacial interaction with cellulose in the composites. Compared with the lower molecular weight, the composites derived from higher molecular weight of PP exhibited stronger tensile strength at the same cellulose content.     

Advanced CPMAS-13C NMR techniques for molecular characterization of size-separated fractions from a soil humic acid

A humic acid extracted from a volcanic soil was subjected to preparative high-performance size-exclusion chromatography (HPSEC) to reduce its molecular complexity and eleven different size fractions were obtained. Cross-polarization magic-angle spinning ¹³C NMR (CPMAS ¹³C NMR) analysis performed with variable contact-time (VCT) pulse sequences showed that the largest molecular-size fractions contained aromatic, alkyl, and carbohydrate-like components. The carbohydrate-like content and the alkyl chain length seemed to decrease with decreasing molecular size. Progressive reduction of aromatic carbon atoms was also observed with decreasing molecular size of the separated fractions. Mathematical treatment of the results from VCT experiments enabled cross polarization (T _CH) and proton spin–lattice relaxation () times to be related to structural differences among the size fractions. The conformational distribution indicated that the eleven size fractions could be allocated to two main groups. The first group, with larger nominal molecular sizes, was characterized by molecular domains with slower local molecular motion. The second group of size fractions, with smaller nominal molecular sizes, was characterized by a larger number of molecular domains with faster local molecular motion. The T _CH and values suggested that either condensed or strongly associated aromatic systems were predominant in the size fractions with the largest apparent molecular dimensions.     

Directed assembly of transition-metal-coordinated molecular loops and squares from salen-type components. Examples of metalation-controlled structural conversion

A series of transition-metal-containing molecular "loops" and "squares" has been prepared via a directed-assembly approach and characterized. The molecular loops were prepared from the reaction of cis-(PEt(3))(2)Pt(OTf)(2) with bis(4-pyridyl)-functionalized free-base salen-type ligands. Zn(II)-metalation of the salen-type ligands in the molecular loops converts the loops to molecular squares. Alternatively, the squares can be obtained by the directed assembly of cis-(PEt(3))(2)Pt(OTf)(2) and bis(4-pyridyl)-functionalized Zn(II)-salen-type ligands. A concentration-dependent dynamic equilibrium between cyclic species was observed when bis(3-pyridyl)-functionalized free-base salen-type ligand was employed in the reaction. Zn(II) or Cr(III) metalation of the free-base ligand shifted the equilibrium to the single dimeric species. The incorporation of multiple reactive metal sites into a single, cavity-containing supramolecular structure points toward catalytic applications for these new assemblies.     

Synthesis of molecular brushes by "grafting onto" method: combination of ATRP and click reactions

Molecular brushes (densely grafted polymers or bottle-brush macromolecules) were synthesized by the "grafting onto" method via combination of atom transfer radical polymerization (ATRP) and "click" reactions. Linear poly(2-hydroxyethyl methacrylate) (PHEMA) polymers were synthesized first by ATRP. After esterification reactions between pentynoic acid and the hydroxyl side groups, polymeric backbones with alkynyl side groups on essentially every monomer unit (PHEMA-alkyne) were obtained. Five kinds of azido-terminated polymeric side chains (SCs) with different chemical compositions and molecular weights were used, including poly(ethylene glycol)-N3 (PEO-N3), polystyrene-N3, poly(n-butyl acrylate)-N3, and poly(n-butyl acrylate)-b-polystyrene-N3. All click coupling reactions between alkyne-containing polymeric backbones (PHEMA-alkyne) and azido-terminated polymeric SCs were completed within 3 h. The grafting density of the obtained molecular brushes was affected by several factors, including the molecular weights and the chemical structures of the linear SCs, as well as the initial molar ratio of linear chains to alkynyl groups. When linear polymers with "thinner" structure and lower molecular weight, e.g., PEO-N3 with Mn = 775 g/mol, were reacted with PHEMA-alkyne (degree of polymerization = 210) at a high molar ratio of linear chains to alkynyl groups in the backbone, the brush copolymers with the highest grafting density were obtained (Y(grafting) = 88%). This result indicates that the average number of SCs was ca. 186 per brush molecule and the average molecular weight of the brush molecules was ca. 190 kg/mol.     

Preparation and characterization of an imprinted monolith by atom transfer radical polymerization assisted by crowding agents

A method based on reverse atom transfer radical polymerization (R-ATRP) and molecular crowding has been used for design and synthesis of monolithic molecularly imprinted polymers (MIPs) capable of recognizing ibuprofen (IBU). 4-Vinylpyridine (4-VP) was used as the functional monomer, and ethylene glycol dimethacrylate (EDMA) was the crosslinking monomer. Azobisisobutyronitrile (AIBN)–CuCl₂–N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA) was used as the initiating system. Compared with conventional radical polymerization-based IBU-MIPs, the imprinting effects of the obtained IBU-MIPs was enhanced, suggesting the merit of combination of reverse ATRP and molecular crowding. In addition, it was found that the polymerization time of the molecularly imprinted monolithic column, the amount of template, the degree of crosslinking, and the composition of mobile phase greatly affected retention of the template and the performance of molecular recognition .

Aqueous RAFT polymerization of acrylamide: A convenient method for polyacrylamide with narrow molecular weight distribution

Controlled and homogeneous free-radical polymerization of acrylamide(AM) in aqueous phase was realized by using S,S'-bis(α,α'-dimethyl-α'-acetic acid)-trithiocarbonate as a reversible addition-fragmentation transfer(RAFT) agent. Linear increases in molecular weight with conversion and narrow molecular weight distribution were observed for polyacrylamide(PAM) throughout the polymerization. By this method, PAMs with controlled molecular weight(up to 1.0 × 10~6) and narrow molecular weight distribution(M_w/M_n 1.2) were prepared. This study provides an effective method for synthesis of PAMs with narrow molecular weight distribution under environmentally friendly conditions.     

Materials Studio软件在“金属”教学中的应用*

以中学化学所涉及的“金属”物质教学内容为例,运用MS分子模拟软件内嵌的Visualizer,Build 及Symmetry property 等3个功能模块,在不同尺度(从埃、纳米、微米到厘米)范围内,实现对“金属原子结构”“金属晶体”及“金属性质(密度)”的连续性可视化展示,帮助学生从原子的视角深入理解化学物质微观结构与宏观性质之间的本质相关性。     

Oxidation of 5-aminouracil with molecular oxygen in aqueous solution in the presence of copper(II) chloride

5-Aminouracil was found to form a six-coordinate copper(II) complex in aqueous solution and undergo oxidation to 5,5,6-trihydroxypyrimidine-2,4(1H,3H)-dione in the presence of molecular oxygen. A scheme was proposed for the fixation and activation of molecular oxygen on six-coordinate copper(II) complex with 5-aminouracil. The effect of the ligand structure on the rate of its oxidation with molecular oxygen in aqueous solution in the presence of copper(II) ions was shown.     

Self-assembly of metal-organic hybrid nanoscopic rectangles

The combination of an amide containing a linear ligand (L1) and an organometallic molecular "clip" (clip-1) leads to the self-assembly of a Pt4 nanoscopic framework representing the first example of a Pt-based molecular rectangle (rectangle-1) incorporating amide functionality. A complementary approach was also followed to prepare a Pd(II)-based molecular rectangle (rectangle-2) by reaction of a donor organic rigid clip (clip-2) and trans-(PEt3)2Pd(OTf)2 as the linear metal acceptor (L2). The Pd(II)-rectangle was characterised by multinuclear NMR and ESI-mass spectroscopy.     

Ferroelectric porous molecular crystal, [Mn3(HCOO)6](C2H5OH), exhibiting ferrimagnetic transition

A porous molecular crystal with guest ethanol molecules, [Mn3(HCOO)6](C2H5OH), was found to be a new type of multifunctional molecular system, which exhibits a ferroelectric transition at 165 K and a ferrimagnetic transition at 8.5 K. [Mn3(HCOO)6](C2H5OH) will give a hint to design "multiferroic" molecular materials where ferroelectric and ferromagnetic orders coexist.     

Solvent effect in cis-1,4 polymerization of 1,3-butadiene by a catalyst based on neodymium

In this work a laboratory polymerization scale process was studied for the production of polybutadiene with high content of cis-1,4 repeating units. A Ziegler-Natta catalytic system based on neodymium versatate (catalyst), diisobutylaluminium hydride (cocatalyst) and tert-butyl chloride (chlorinating agent) was used. The influence of solvent nature (pure grade) and possible contaminants (electron donors) in a recovered solvent from a butadiene-styrene anionic polymerization industrial plant on the stereoselectivity and catalytic activity, molecular weight and molecular weight distribution of the resultant polybutadienes was studied. The polymers were characterized by infrared spectroscopy and size exclusion chromatography. Polybutadienes with cis-1,4 units content in the range of 99-98% were produced. The polymers weight-average molecular weight, , varied from 2.23 × 10⁵ to 4.47 × 10⁵ and the molecular weight distribution, MWD, from 3.1 to 5.1.     

Designed self-assembly of molecular necklaces

This paper reports an efficient strategy to synthesize molecular necklaces, in which a number of small rings are threaded onto a large ring, utilizing the principles of self-assembly and coordination chemistry. Our strategy involves (1) threading a molecular "bead" with a short "string" to make a pseudorotaxane and then (2) linking the pseudorotaxanes with a metal complex with two cis labile ligands acting as an "angle connector" to form a cyclic product (molecular necklace). A 4- or 3-pyridylmethyl group is attached to each end of 1,4-diaminobutane or 1,5-diaminopentane to produce the short "strings" (C4N4(2+), C4N3(2+), C5N4(2+), and C5N3(2+)), which then react with a cucurbituril (CB) "bead" to form stable pseudorotaxanes (PR44(2+), PR43(2+), PR54(2+), and PR53(2+), respectively). The reaction of the pseudorotaxanes with Pt(en)(NO(3))(2) (en = ethylenediamine) produces a molecular necklace [4]MN, in which three molecular "beads" are threaded on a triangular framework, and/or a molecular necklace [5]MN, in which four molecular "beads" are threaded on a square framework. Under refluxing conditions, the reaction with PR44(2+) or PR54(2+) yields exclusively [4]MN (MN44T or MN54T, respectively), whereas that with PR43(2+) or PR53(2+) produces exclusively [5]MN (MN43S or MN53S, respectively). The products have been characterized by various methods including X-ray crystallography. At lower temperatures, on the other hand, the reaction with PR44(2+) or PR54(2+) affords both [4]MN and [5]MN. The supermolecules reported here are the first series of molecular necklaces obtained as thermodynamic products. The overall structures of the molecular necklaces are strongly influenced by the structures of pseudorotaxane building blocks, which is discussed in detail on the basis of the X-ray crystal structures. The temperature dependence of the product distribution observed in this self-assembly process is also discussed.