Optimized biorecognition of cytochrome c 551 and azurin immobilized on thiol-terminated monolayers assembled on Au(111) substrates

Molecular recognition between two redox partners, azurin and cytochrome c 551, is studied at the single-molecule level by means of atomic force spectroscopy, after optimizing azurin adsorption on gold via sulfhydryl-terminated alkanethiol spacers. Our experiments provide evidence of specific interaction between the two partners, thereby demonstrating that azurin preserves biorecognition capability when assembled on gold via these spacers. Additionally, the measured single-molecule kinetic reaction rate results are consistent with a likely transient nature of the complex. Interestingly, the immobilization strategy adopted here, which was previously demonstrated to favor electrical coupling between azurin (AZ) and the metal electrode, is also found to facilitate AZ interaction with the redox partner, if compared to the case of AZ directly adsorbed on bare gold. Our findings confirm the key role of a well-designed immobilization strategy, capable of optimizing both biorecognition capabilities and electrical coupling with the conductive substrate at the single-molecule level, as a starting point for advanced applications of redox proteins for ultrasensitive biosensing.     

Functional metalloproteins integrated with conductive substrates: detecting single molecules and sensing individual recognition events

In the past decade, there has been significant interest in the integration of biomaterials with electronic elements: combining biological functions of biomolecules with nanotechnology offers new perspectives for implementation of ultrasensitive hybrid nanodevices. In particular, great attention has been devoted to redox metalloproteins, since they possess unique characteristics, such as electron-transfer capability, possibility of gating redox activity, and nanometric size, which make them appealing for bioelectronics applications at the nanoscale. The reliable connection of redox proteins to electrodes, aimed at ensuring good electrical contact with the conducting substrate besides preserving protein functionality, is a fundamental step for designing a hybrid nanodevice and calls for a full characterization of the immobilized proteins, possibly at the single-molecule level. Here, we describe how a multitechnique approach, based on several scanning probe microscopy techniques, may provide a comprehensive characterization of different metalloproteins on metal electrodes, disclosing unique information not only about morphological properties of the adsorbed molecules but also about the effectiveness of electrical coupling with the conductive substrate, or even concerning the preserved biorecognition capability upon adsorption. We also show how the success of an immobilization strategy, which is of primary importance for optimal integration of metalloproteins with a metal electrode, can be promptly assessed by means of the proposed approach. Besides the characterization aspect, the complementary employment of the proposed techniques deserves major potentialities for ultrasensitive detection of adsorbed biomolecules. In particular, it is shown how sensing of single metalloproteins may be optimized by monitoring the most appropriate observable. Additionally, we suggest how the combination of several experimental techniques might offer increased versatility, real-time response, and wide applicability as a detection method, once a reproducible correlation among signals coming from different single-molecule techniques is established.     

碳税机制下考虑不同低碳策略的动态博弈模型及复杂性研究

考虑碳排放税,建立双寡头制造商分别实施废品回收和绿色低碳广告投入策略的动态博弈模型。通过系统稳定域,分岔图,功率谱等分析了博弈模型纳什均衡解处的稳定性及参数对系统稳定域的影响,同时对系统的复杂性特征进行了研究。结果表明,消费者回收价格敏感性增加会使整个系统稳定域缩小,而绿色低碳广告投入水平增加只会使实施该策略的企业自身稳定域扩大;当制造商价格调整速度过快时,系统会进入混沌状态;混沌状态下,对比实施广告策略的制造商,实施废品回收策略的制造商价格调整行为对市场造成的震荡更大。最后使用反馈控制策略对系统混沌状态进行了有效的控制,研究结果对制造商低碳策略选择及价格决策有着较好的借鉴意义。     

Lévy statistics of vibrational mode fluctuations of single molecules from surface-enhanced Raman scattering

Surface-enhanced Raman spectra of a single Fe-protoporphyrin IX molecule display drastic fluctuations in frequency and intensity. When analyzed in their temporal evolution, the vibrational modes of the molecule undergo an on-off switching behavior that is shown to follow a Lévy statistics. Such a time dependent process may encode both the dynamics of the molecule-environment interactions and the intrinsic gating or activation of the mode emission mechanism.     

Temperature dependence of theg=6 EPR linewidth in high spin FeIII myoglobin samples

The temperature dependence of theg=6 line of high spin FeIII aqueous mixed water-glycerol myoglobin samples has been investigated by EPR spectroscopy. The trend with the temperature of the linewidth has been analyzed by taking into account both a temperature-independent contribution from the frozen structural heterogeneity (conformational substate distribution) and the relaxation processes. The temperature-dependent line broadening process due to the spin-lattice relaxation has been singled out by simulation of the experimental data and put into relationship to the density of the vibrational states. The effect on the vibrational modes of the protein-solvent system, as induced by the addition of large amount of the glass-making solvent, glycerol, is discussed.     

Optical Properties,Conductivity and Structure of the DTT-TCNQ CT Complex

Abstract

The crystal structure, the optical spectra and electrical conductivity of dithieno(3,2-b; 2′,3′-d)thiophene-tetracyanoquinodimethane (DTT-TCNQ) charge-transfer complex have been measured. DTT-TCNQ crystallizes in the monoclinic space group P2₁/c with a = 7.206(2), b = 7.574(2), c = 32.324(9), β - 92.18(4)°, Z - 4, and the donor and acceptor molecules are arranged in alternated stacks.

The low conductivity (a = 10^?2 S cm^?1 for the single crystal, along the stacking axis a) is characteristic of a semiconductor with activation energy of .61-.76 eV, and is related to the alternate stack structure.

Despite the poor condctivity of the DTT-TCNQ CT complex we estimated, from structure and IR data, a low degree of ionicity (p = .2–.3) which characterizes the DTT molecule as an interestign donor.

The polarized IR spectra shows the effect of vibronic activation of some of the a_g modes of TCNQ.     

Evaluation and preliminary measurement of the interaction of a dynamical gravitational near field with a cryogenic gravitational wave antenna

We present a detailed analysis of the effect of the gravitational field generated by a small rotating quadrupole on a graviational wave antenna and we report on the preliminary measurement of this effect on the Explorer 2270 kg cryogenic gravitational wave antenna of the Rome group. The induced signal had an amplitude twenty times larger than the detector noise when the antenna was equipped with an FET amplifier and was easily detected without requiring integration in time. We remark that with this method we were able to make an absolute calibration of a gravitational wave antenna.     

On regularity of block triangular fuzzy matrices

Necessary and sufficient conditions are given for the regularity of block triangular fuzzy matrices. This leads to characterization of idempotency of a class of triangular Toeplitz matrices. As an application, the existence of group inverse of a block triangular fuzzy matrix is discussed. Equivalent conditions for a regular block triangular fuzzy matrix to be expressed as a sum of regular block fuzzy matrices is derived. Further, fuzzy relational equations consistency is studied.     

Z4-Kerdock Codes, Orthogonal Spreads, and Extremal Euclidean Line-Sets

When m is odd, spreads in an orthogonal vector space of type⁺(2m + 2,2) are related to binary Kerdock codes and extremalline-sets in 2^{m + 1} with prescribed angles. Spreads in a 2m-dimensionalbinary symplectic vector space are related to Kerdock codesover Z₄ and extremal line-sets in with prescribed angles. These connections involve binary, realand complex geometry associated with extraspecial 2-groups.A geometric map from symplectic to orthogonal spreads is shownto induce the Gray map from a corresponding Z₄-Kerdock codeto its binary image. These geometric considerations lead tothe construction, for any odd composite m, of large numbersof Z₄-Kerdock codes. They also produce new Z₄-linear Kerdockand Preparata codes. 1991 Mathematics Subject Classification:primary 94B60; secondary 51M15, 20C99.     

Cyan-Emitting Cu(I) Complexes and Their Luminescent Metallopolymers

Copper complexes have shown great versatility and a wide application range across the natural and life sciences, with a particular promise as organic light-emitting diodes. In this work, four novel heteroleptic Cu(I) complexes were designed in order to allow their integration in advanced materials such as metallopolymers. We herein present the synthesis and the electrochemical and photophysical characterisation of these Cu(I) complexes, in combination with ab initio calculations. The complexes present a bright cyan emission (λ_em ~ 505 nm) in their solid state, both as powder and as blends in a polymer matrix. The successful synthesis of metallopolymers embedding two of the novel complexes is shown. These copolymers were also found to be luminescent and their photophysical properties were compared to those of their polymer blends. The chemical nature of the polymer backbone contributes significantly to the photoluminescence quantum yield, paving a route for the strategic design of novel luminescent Cu(I)-based polymeric materials.