Ce-Doped Smart Adsorbentswith Photoresponsive Molecular Switches for Selective Adsorption and Efficient Desorption

Achieving efficient adsorption and desorption processes by controllably tuning the properties of adsorbents at different technical stages is extremely attractive.However,it is difficult for traditional adsorbents to reach the target because of their fixed active sites.Herein,we report on the fabrication of a smart adsorbent,which was achieved by introducing photoresponsive azobenzene derivatives with cis/trans isomers to Ce-doped mesoporous silica.These photoresponsive groups serve as “molecular switches”by sheltering and exposing active sites,leading to efficient adsorption and desorption.Ce is also doped to provide additional active sites in order to enhance the adsorption performance.The results show that the cis isomers effectively shelter the active sites,leading to the selective adsorption of methylene blue(MB)over brilliant blue(BB),while the trans isomers completely expose the active sites,resulting in the convenient release of the adsorbates.Both selective adsorption and efficient desorption can be realized controllably by these smart adsorbents through photostimulation.Moreover,the performance of the obtained materials is well maintained after five cycles.

Synthesis of Hymecromone Derivatives Containing Chiral 1,1'-Bi-2-naphthyl Moiety for Dual-mode Molecular Switch

Some hymecromone derivatives containing chiral 1,1'-bi-2-naphthyl moiety were synthesized and their photodimerizations were investigated. It was found that fluorescence intensity and optical rotation of the new chiral hymecromone derivatives could be regulated by light. This property has potential significance for developing a new type of dual-mode molecular switch.

Characterization of a Redox-responsive Molecular Switch Based on Dibenzo[1,2]dithiine Using DFT

Structural and electronic properties of a bistable redox-responsive molecular switch based on dibenzo[1,2]dithiine （PSBH） were studied using the DFT-B3LYP/6-31G＊ method. The results confirmed that the electrical conductivity of the closed form of considered molecular switch is higher than that of the open form. NBO electric charges on heavy atoms of biphenyl unit revealed that the positive charge on sulfur atoms reinforced, which caused the collapse of disulfide bond.

pH-Controlled DNA Molecular Switch Using Minidumbbell

DNA is an attractive biomaterial for constructing nanomachines and nanomaterials owing to their self-recognition and self-assembly properties.In addition to the well-known double helical structures,DNA molecules can also form a variety of unusual structures like hairpins,triplexes and quadruplexes.These unusual DNAs sometimes have advantages over double helical DNAs in constructing nanomachines such as enhanced thermodynamic stability and higher sensitivity to external stimuli,which made them as promising motifs in recenttwo decades.Regardless of how complicated DNA-based nanomachines are,the fundamental concept in these nanomachines is based on a proper design and usage of DNA molecular switch.Among the reported DNA molecular switches,pH-controlled systems show great potentials in drug delivery and cellular pH sensing.Up to now,most of the reported pH-controlled molecular switches used i-motif or triplex DNAs.However,owing to the relatively long sequence requirement for the formation of i-motif and triplex DNAs,an invading DNA strand needs to be added to activate the molecular switch,and thus DNA wastes will be generated into the system and a full structural conversion will usually take a relatively long time of minutes to hours.To overcome the disadvantages of DNA waste generation and slow kinetics,molecular switches using smaller-size,thermodynamically stable and pH-sensible unusual DNA structures will have the advantages of easier manipulation and faster kinetics.Recently,we discovered a new type of unusual DNA structure called the minidumbbell(MDB)which is formed by a single-strand 8-nucleotide sequence.The MDB is composed of two type II tetraloops in which the first and fourth loop residues form loop-closing base pairs,the second loop residues fold into the minor groove to form base-base stacking or mispairing interactions,and the third loop residues stack on their nearby loop-closing base pairs.In particular,the MDB formed by a sequence containing two CCTG repeats has a relatively low melting temperature(Tm)of^22℃at pH 7.0,whereas its Tm can be significantly increased to^46℃at pH 5.0 due to the formation of a three hydrogen bond hemiprotonated C+·C mispair in the minor groove.This MDB,when combined with its complementary sequence,shows instant and complete structural conversions when the pH switches between 5.0 and 7.0 without using an invading DNA strand,serving as a simple and efficient pH-controlled molecular switch.In order to allow the incorporation of fluorophores to the two termini of the MDB,we aim to design a thermodynamically more stable MDB structure in this study.Through a rational design by introducing hydrophobic interactions to the MDB formed by the sequence containing two CCTG repeats at pH 5.0,we obtained an MDB structure with a record-high Tm of^62℃.Furthermore,this MDB was found to exist stably in the presence of 5’and 3’-overhanging residues,revealing its capability of being attached with fluorophores or other functional groups,and thus making it potentially a versatile pH-controlled molecular switch for designing nanomachines and nanomaterials.

A Label-Free Colorimetric Aptasensor Containing DNA Triplex Molecular Switch and AuNP Nanozyme for Highly Sensitive Detection of Saxitoxin

Saxitoxin(STX),one of the most toxic paralytic shellfish poisons discovered to date,is listed as a required item of aquatic product safety inspection worldwide.However,conventional detection methods for STX are limited by various issues,such as low sensitivity,complicated operations,and ethical considerations.In this study,an aptamer-triplex molecular switch(APT-TMS)and gold nanoparticle(AuNP)nanozyme were combined to develop a label-free colorimetric aptasensor for the rapid and highly sensitive de-tection of STX.An anti-STX aptamer designed with pyrimidine arms and a purine chain was fabricated to form an APT-TMS.Specific binding between the aptamer and STX triggered the opening of the switch,which causes the purine chains to adsorb onto the surface of the AuNPs and enhances the peroxidase-like activity of the AuNP nanozyme toward 3,3’,5,5’-tetramethylbenzidine.Under optimized conditions,the proposed aptasensor showed high sensitivity and selectivity for STX,with a limit of detection of 335.6 pmol L^(−1) and a linear range of 0.59-150 nmol L^(−1).Moreover,good recoveries of 82.70%-92.66%for shellfish and 88.97%-106.5%for seawater were obtained.The analysis could be completed within 1 h.The proposed design also offers a robust strategy to achieve detection of other marine toxin targets by altering the corresponding aptamers.

Effect of Chirality on the Electronic Transport Properties of the Thioxanthene-Based Molecular Switch

Based on the nonequilibrium Green function method and density functional theory calculations, we theoretically investigate the effect of chirality on the electronic transport properties of thioxanthene-based molecular switch. The molecule comprises the switch which can exhibit different chiralities, that is, cis-form and trans-form by ultraviolet or visible irradiation. The results clearly reveal that the switching behaviors can be realized when the molecule converts between cis-form and trans-form. ~urthermore, the on-off ratio can be modulated by the chirality of the carbon nanotube electrodes. The maximum on-off ratio can reach 109 at 0.4 V for the armchair junction, suggesting potential applications of this type of junctions in future design of functional molecular devices.

A Study on the Molecular Switch of Gene Expression of the Mouse Heart Nuclear DNA Fragments

It is observed by in situ stain that LDH (1 5) ...nNAD + can probably enter the nucleopore and can be bound bound specifically with the genes that encode them. During the in vitro expression, the dilution of heart nuclear DNA fragments could enhance the expression activity of LDH/DNA and the amount of expressed LDH (1 5) is in proportion to the amount of dissociable LDH (1 5) on the LDH/DNA. With the integration of 14C Leu to the proteins, it is also observed that the addition of LDH (1 5) ...nNAD + can suppress the in vitro expression activity of LDH/DNA. AFM observation shows that the regulation sequence at the both ends of active genes may be bound with such active factors as proteins encoded by the genes which probably is the main molecular switch of gene expression and regulation we have been always searching for. Our work shows the prospective application of the combination of AFM and isotope labeling in the research of biological reaction.

Current–Voltage Characteristics of the Aziridine-Based Nano-Molecular Wires: a Light-Driven Molecular Switch

Using nonequilibrium Green＇s function formalism combined first-principles density functional theory, we analyze the transport properties of a 4,4-dimethyl-6-（4-nitrophenyl）-2-phenyl-3,5-diaza-bicyclo[3.1.0]hex-2-ene molecular optical switch. The title molecule can convert between closed and open forms by visible or ultraviolet irradiation. The I-V characteristics, differential conductance, on-off ratio, electronic transmission coefficients, spatial distribution of molecular projected self-consistent Hamiltonian orbitals, HOMO-LUMO gaps, effect of electrode materials Y（111）（Y =Au, Ag and Pt） on electronic transport and different molecular geometries corresponding to the closed and open forms through the molecular device are discussed in detail. Based on the results, as soon as possible the open form translates to the closed form, and there is a switch from the ON state to the OFF state（low resistance switches to high resistance）. Theoretical results show that the donor/acceptor substituent plays an important role in the electronic transport of molecular devices. The switching performance can be improved to some extent through suitable donor and acceptor substituents.

银-二芳基乙烯化合物的合成及其光致变色性质的研究

金属介导的分子开关配合物在有机光电功能材料及分子器件等领域具有广阔的应用前景。本工作通过配位导向机制将金属离子Ag I与二芳基乙烯开关L结合,制备一种银-二芳基乙烯配位化合物[L-AgNO_(3)]_(2)(CHCl_(3))_(2)(Ag-L)。其单晶结构表明,中心金属离子Ag I与L上不同位置的N原子发生配位作用形成一个扭曲的四面体。通过红外光谱(IR)及核磁共振氢谱(1H NMR)对其结构进行表征,利用紫外-可见分光光谱仪(UV-Vis)研究Ag-L的光致变色行为,探索了其在不同介质中的开闭环过程。一系列研究结果表明,Ag-L化合物在二氯甲烷溶液和聚甲基丙烯酸甲酯(PMMA)中均具有良好的可逆光致变色性质。

偶氮苯基小分子光控聚N-异丙基丙烯酰胺在离子液体中的自组装

偶氮苯基材料因其具有可逆的光致顺反异构特性,可调控聚合物的自组装行为而受到广泛关注。采用不同结构且广泛商业化的偶氮苯基小分子(偶氮苯(AZO)、对羟基偶氮苯(AZO-OH)、对氨基偶氮苯(AZO-NH2)、二甲基黄[AZO-N(CH_(3))_(2)])作为光分子开关,控制聚N-异丙基丙烯酰胺(PNIPAm)在1-乙基-3-甲基咪唑双(三氟甲基磺酰基)亚胺([C2mim][NTf_(2)])离子液体中的自组装行为,探讨不同偶氮苯基末端基元对于PNIPAm自组装相行为的影响。结果表明,偶氮苯基小分子均能有效调控PNIPAm在[C2mim][NTf_(2)]离子液体中的相变响应行为,但不同的末端基元对于PNIPAm的相变温度及相变区间影响甚微。结合原位变温红外谱图分析可知,紫外光照强化了PNIPAm与离子液体之间的相互作用,从而抑制了PNIPAm侧链间的相互聚集,这将促进紫外光照条件下“溶剂化”效应的发生,可获得更低的相变温度。

Electrically Driven Nonresonant Single Molecular Switches

Electrical switching of a single-molecule junction provides a practical module to perform sophisticated operations in electronic devices.However,designing an all-electrically-driven molecular switch is a great challenge.Here,we experimentally and theoretically investigated the charge transport characteristics of isoindigo(ISO)-molecules at the single-molecule level using the scanning tunneling microscope break junction technique.We find that the single-molecule junctions of ISO-molecules display bias voltage-driven switching characteristics.These switches are realtime,reversible,and nondestructive under low-bias voltages.Experimental results show that the mechanism of the switch is not the transition from nonresonant charge transport to resonant charge transport,but it is the shift of the frontier orbital energy levels of ISO-molecules and the change of the interfacial electronic coupling with bias voltage.Our results will advance the design of high-performance bias voltage-driven molecular switches.

A theoretical investigation on anomalous switching of single-stranded deoxyribonucleic acid(ssDNA) monolayers by water vapor

In this paper, we use a molecular theory to study the anomalous switching of ssDNA monolayers. Here, both ssDNA- water and water-water hydrogen bonds and their explicit coupling to the ssDNA conformations are considered. We find that hydrogen bonding becomes a key element in inducing the anomalous switching of ssDNA monolayers. This finding accords well with the experimental observations. Based on our theoretical model, we predict that the anomalous switching induced by water vapor will be applicable to a wide range of hydrogen bonds polymers, and ssDNA-water hydrogen bonds and water-water hydrogen bonds hybridization will lead to the hydrogen-bond network formation of 3D ssDNA monolayers.

Structure and switching of single-stranded DNA tethered to a charged nanoparticle surface

Using a molecular theory, we investigate the temperature-dependent self-assembly of single-stranded DNA（ss DNA）tethered to a charged nanoparticle surface. Here the size, conformations, and charge properties of ss DNA are taken into account. The main results are as follows： i） when the temperature is lower than the critical switching temperature, the ss DNA will collapse due to the existence of electrostatic interaction between ss DNA and charged nanoparticle surface; ii）for the short ss DNA chains with the number of bases less than 10, the switching of ss DNA cannot happen, and the critical temperature does not exist; iii） when the temperature increases, the electrostatic attractive interaction between ss DNA and charged nanoparticle surface becomes weak dramatically, and ss DNA chains will stretch if the electrostatic attractive interaction is insufficient to overcome the elastic energy of ss DNA and the electrostatic repulsion energy. These findings accord well with the experimental observations. It is predicted that the switching of ss DNA will not happen if the grafting densities are too high.

Molecular dynamics simulation of ion selectivity traits of nickel hexacyanoferrate thin films

The ion selectivity of nickel hexacyanoferrate thin film to alkali cations in ESIX (electrochemically switched ion exchange) processes was investigated using molecular dynamics(MD) techniques; water and cation (Na+ and Cs+) intercalation, configuration, and dynamics in reduced nickel hexacyanoferrate structures with different cation combinations were studied and compared with the experimental results. In the simulations, water was represented by an extended simple point-charge(SPC/E) model, and all other atomic interactions were represented by a universal force field(UFF). The potential energies of various cations combination (Cs+ and Na+) in reduced i-NiHCF and 1 mol/L Cs/NaCl mixed solution were obtained. In most cases, the total potential energy of the solid is reduced when water is intercalated into the various reduced NiHCF structures. Combining the solid and the solution simulation results, it is shown that the solid composition of 3Cs+/1Na+ is the stablest structure form (NaCs3Ni4[Fe(CN)6]3) over a range of solution compositions.

PHOTOSWITCHABLE NANOFLUOROPHORES FOR INNOVATIVE BIOIMAGING

Photosensitive fluorescent probes have become powerful tools in chemical biology and molecular biophysics,which are used to investigate cellular processes with high temporal and spatial resolution.Accordingly,photosensitive fluorescent probes,including photoactivatable,photoconvertible,and photoswitchable fluorophores,have been extensively developed during the past decade.The photoswitchable fluorophores have received much attention because they highlight cellular events clearly.This minireview summarizes recent advances of using reversibly photoswitchable fluorophores and their applications in innovative bioimaging.Photoswitchable fluorophores include photoswitchable fluorescent proteins,photoswitchable fluorescent organic molecules(dyes),and photoswitchable fluorescent nanoparticles.Several strategies have been developed to synthesize photoswitchable fluorophores,including engineering combination proteins,chemical synthesis,polymerization,and self-assembly.Here we concentrate on polymer nanoparticles with optically switchable emission properties:either fluorescence on/offor dualalternating-color fluorescence photoswitching.The essential mechanisms of fluorescence photoswitching enable different types of photoswitchable fluorophores to change emission intensity or wavelength(color)and thus validating the basis of the fluorescence on/offor dual-color photoswitching design.Generally the possible applications of any fluorophores are to label biological targets,followed by specific imaging.The newly developed photoswitchable fluorophores enable super-resolution fluorescence imaging because of their photosensitive emission.Finally,we summarize the important area regarding future research and development on photoswitchable fluorescent nanoparticles.

Ferroelectric Liquid Crystal Optical Switches

The dynamic response of molecular orientation, and the temperature and pulse shape dependences of the switching behavior in ferroelectric liquid crystal are described. The switching speed and the surface energy of ferroelectric liquid crystal are given.

微惯性开关制作过程中界面结合强度研究

在利用微电铸工艺制作惯性开关的过程中,经常会出现由于界面结合强度低而引起的铸层翘起问题。微电铸层与基板的界面结合强度低会降低微开关的制作成品率、延长制作周期、增加制作成本。针对这一问题,本文从界面钝化膜的角度,采用了“电解活化去除钝化膜”和“引入Cu过渡层”的方法。为探究钝化膜对界面结合强度的影响,通过Materials Studio软件对不同钝化膜去除率模型的界面结合能进行仿真计算,计算结果表明钝化膜去除率越高越有利于界面结合强度的提高,在完全去除钝化膜后界面结合强度提高了197%;为探究过渡金属对界面结合强度的影响,分别以Cu,Cr,Ti作为过渡层,与不锈钢基板和镍铸层建立结合层体系,计算体系的结合能,计算结果表明Cu与基板、Cu与铸层的结合能最高,与未引入过渡金属相比,引入Cu后界面结合强度提高了81%。在仿真研究结果的基础上,开展了电解活化实验,通过电解活化法去除了基板表面的钝化膜,实验结果表明:电解活化区域铸层的界面结合强度明显高于未活化区域铸层的界面结合强度;同时开展了铜过渡层实验,对比了有无Cu过渡层的界面结合强度,实验结果表明:引入Cu后,铸层的界面结合强度明显提高。在上述仿真和实验结果的基础上,制作出尺寸为23 mm×20 mm、总高度为900μm的微惯性开关。

基于1,2-二氰基苯/聚合物复合材料的高耐久性有机阻变存储器

本文报道了一种基于1,2-二氰基苯(O-DCB)与聚(3-己基噻吩)(P3HT)复合薄膜的高耐久性有机阻变存储器(ORSM).ORSM表现出非易失型和双极性存储特性,电流开关比(I_(on/off))超过10^(4),耐久性高达400次,保持时间为10^(5)s,V_(set)和V_(reset)分别为-6.9 V和2.6 V.器件的阻变机理是陷阱电荷的俘获与去俘获,即负偏压或正偏压诱导电荷陷阱的填充和抽离过程,导致电荷传输方式的改变,从而产生高低电阻间的切换.器件的高耐久性一方面是由于O-DCB较小的分子尺寸和较好的溶解性形成了均匀分布且稳定的电荷陷阱,另一方面是由于O-DCB较好的分子平面促进了其与P3HT共轭链的相互作用.该研究为高耐久性ORSM的实现提供了一种有效途径,加快了ORSM的商业化应用进程.

给体-受体型二维共轭聚合物的分子共平面性对阻变均一性的影响

有机忆阻器具有超快速度、超低功耗、非易失性存储等优势,有希望成为突破当前冯·诺依曼瓶颈和摩尔定律极限的关键电子元器件。利用2,6-双(三甲基锡)-4,8-双(5-己基-2-噻吩)-苯并[1,2-b:4,5-b’]二噻吩,4,9-二溴-6,7-双苯基[1,2,5]噻二唑-[3,4-g]喹喔啉和4,8-二溴苯并[1,2-c:4,5-c']双[1,2,5]噻二唑,通过Stille偶联法合成得到两种新型二维共轭给体-受体型聚合物pBDTT-PTQx和pBDTT-BBT,通过选取位阻较小的取代基、长度较短的烷基链和强推拉电子效应的共轭给体-受体单元优化分子共平面性,并对比研究了共平面性对材料阻变特性的影响。两种材料均具有高鲁棒性的Flash型阻变行为,可循环擦写100圈以上,其中pBDTT-BBT具有更好的分子共平面性,器件表面均方粗糙度仅为1.71 nm,开/关电压的扰动系数仅为9.4%和6.7%,高/低阻态的扰动系数为13.7%和9.4%,相较于PBDTT-PTQx,开/关电压与高/低阻值的稳定性和均一性获得很大提升。