New RNA labeling methods offer dramatic sensitivity enhancements in 2H NMR relaxation spectra

A new labeling strategy is presented that greatly facilitates the measurement of 2H spin relaxation rates in RNA molecules as a probe of pico- to nanosecond time scale dynamics. In this labeling scheme the sugar positions are uniformly 13C-labeled, with position 2' protonated and all other sites on the sugar deuterated. Pulse sequences are presented for measurement of 2H R1 and R2 relaxation rates at positions 1', 3', and 4' with sensitivity gains that are on the order of 5-fold relative to previous methods that employed random fractional deuteration. The improved sensitivity is transformative and facilitates the study of motion in moderately sized RNA molecules with good sensitivity. The utility of the approach is demonstrated with an application to HIV-2 TAR, where the site-specific measures of molecular dynamics at sugar positions obtained here complement previous studies of dynamics at aromatic sites in the molecule.     

Measurement of long-range 1H-19F scalar coupling constants and their glycosidic torsion dependence in 5-fluoropyrimidine-substituted RNA

Long-range scalar 5J(H1',F) couplings were observed in 5-fluoropyrimidine-substituted RNA. We developed a novel S3E-19F-alpha,beta-edited NOESY experiment for quantitation of these long-range scalar 5J(H1',F) couplings, where the J-couplings can be extracted from inspection of intraresidual (H1',H6) NOE cross-peaks. Quantum chemical calculations were exploited to investigate the relation between scalar couplings and conformations around the glycosidic bond in oligonucleotides. The theoretical dependence of the observed 5J(H1',F) couplings on the torsion angle chi can be described by a generalized Karplus relationship. The corresponding density functional theory (DFT) analysis is outlined. Additional NMR experiments facilitating the resonance assignments of 5-fluoropyrimidine-substituted RNAs are described, and chemical shift changes due to altered shielding in the presence of fluorine-19 (19F) are presented.     

Circular‐Dichroism Studies on Artemisinin and Epiartemisinin and Their β‐Cyclodextrin Complexes in Solution

The circular dichroism (CD) spectra of the powerful antimalarian active principle artemisinin (ART; 1 ) from Artemisia annua, and of epiartemisinin (EPI, 2), its C(7) epimer, were studied in solution in the presence and absence of β‐cyclodextrin (β‐cd). A significant inversion of sign in the region of the second electronic transition was detected. The rotational strengths were successfully calculated within the time‐dependent density functional theory (DFT), which enabled us to establish a correlation between the molecular recognition and the biological acitivities of the two isomers.     

Evaluation of K–H3O jarosite as thermal witness material

The scope of this work was the assessment of thermo-oxidative deterioration, hydrothermal stability, and crystalline zone deterioration of some bookbinding leathers from some religious books published in XVIII century stored in Romanian libraries. In this purpose, the following thermal analysis methods were employed: thermogravimetry/derivative thermogravimetry (TG/DTG), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). The thermo-oxidative damage of investigated leathers was characterized by the rate of the first thermo-oxidation process put in evidence in TG/DTG curves recorded in static air atmosphere. The hydrothermal stability was characterized by shrinkage temperature determined by DSC analysis of leathers in water excess. The damage of the crystalline zone of leathers was determined by DSC in nitrogen flow and DMA analyses. The qualitative damage for each leather and each kind of degradation was evaluated using the criteria resulted by thermal analysis of a large number of collagen-based materials (pure collagens, new and old parchments and leathers). The obtained results could be used for finding the best possible methods for preservation and/or restoration of the investigated bookbinding leathers.     

Two-level structured self-adaptive surfaces with reversibly tunable properties

We report a route to fabricate two-level structured self-adaptive surfaces (SAS) of polymer materials. The first level of structure is built by a rough polymer film that consists of needlelike structures of micrometer size. The second level of structure is formed by the nanoscopic self-assembled domains of a demixed polymer brush irreversibly grafted onto the needles. By exposing the surface to solvents that are selective to one of the components of the brush, we reversibly tune the surface properties. The large-scale surface structure amplifies the response and enables us to control wettability, adhesion, and chemical composition of the surface over a wide range.     

A Highly Luminescent Tetramer from a Weakly Emitting Monomer: Acid‐ and Redox‐Controlled Multiple Complexation by Cucurbit[7]uril

The tetrahedral, shape‐persistent molecule 1 ⁴⁺, containing four pyridylpyridinium units connected through a central carbon atom, exhibits unexpected photophysical properties including a substantially redshifted absorption (2350 cm^?1) and a very strong fluorescence (Φ_em=40 %), compared with the monomer 2 ⁺ (Φ_em=0.4 %). Density functional theory calculations on the structure and spectroscopic properties of 1 ⁴⁺ and 2 ⁺ show that exciton interactions, homoconjugation, and orbital nature account for the observed differences in their photophysical properties. The protonated tetramer binds four cucurbit[7]uril molecules and the host/guest interactions can be controlled by chemical (acid/base) as well as redox stimuli.     

Synchronization of neurons in micro-electrode array cultures

A lot of methods were created in last decade for the spatio-temporal analysis of multi-electrode array (MEA) neuronal data sets. In this paper we show how a new simple analysis approach that considers the total network activity, is able to show interesting neuronal network system dynamical features. In particular, we perform two different analyses: a neuronal connectivity examination studying networks at different days in vitro (div) and an analysis of the long per- iod effects of the administration of two common neuroactive drugs, Tetrodotoxin (TTX) and D-2-amino-5-phosphonovalerate (AP5), to spontaneously spiking mature neuronal networks. Our analysis is performed considering burst topology, i.e., cataloguing network bursts as Global (if they involve more than the 25% of the MEA channels) or Local (if less that 25%). In the first analysis, this division allows to understand the network connectivity developments. The networking increases from div 1 to 6 building up an undifferentiated highly connected network. From div 6 to 10 the networking decreases (pruning) till reaching a plateau in a small-world like organization. The second analysis highlights substantial differences between long period effects of TTX and AP5. Results show that AP5, selectively blocking NMDA receptors and inhibiting long term potentiation, is unable to produce activity twisting in a network that already reached a developmental plateau, but it is able to desynchronize sub-network (Local) activity. TTX, on the other side, blocking any type of electrical communication among neurons, acts on the whole network synchronization. The important activity increment in the post-TTX epoch (+66%), together with the Global activity explosion, suggests the possibility of a long-term inhibitory-synapse depression mechanism.     

Some results on starlike trees and sunlike graphs

A tree is called starlike if it has exactly one vertex of degree greater than two. In [4] it was proved that two starlike treesG andH are cospectral if and only if they are isomorphic. We prove here that there exist no two non-isomorphic Laplacian cospectral starlike trees. Further, letG be a simple graph of ordern with vertex setV(G)={1,2, …,n} and letH={H ₁,H ₂, ...H _n } be a family of rooted graphs. According to [2], the rooted productG(H) is the graph obtained by identifying the root ofH _i with thei-th vertex ofG. In particular, ifH is the family of the paths $P_{k_1 } , P_{k_2 } , ..., P_{k_n } $ with the rooted vertices of degree one, in this paper the corresponding graphG(H) is called the sunlike graph and is denoted byG(k ₁,k ₂, …,k _n ). For any (x ₁,x ₂, …,x _n ) ∈I _* ⁿ , whereI _*={0,1}, letG(x ₁,x ₂, …,x _n ) be the subgraph ofG which is obtained by deleting the verticesi ₁, i₂, …,i _j ∈ V(G) (0≤j≤n), provided that $x_{i_1 } = x_{i_2 } = ... = x_{i_j } = 0$ . LetG(x ₁,x ₂,…, x _n] be the characteristic polynomial ofG(x ₁,x ₂,…, x _n ), understanding thatG[0, 0, …, 0] ≡ 1. We prove that $$G[k_1 , k_2 ,..., k_n ] = \Sigma _{x \in ^{I_ * ^n } } \left[ {\Pi _{i = 1}^n P_{k_i + x_i - 2} (\lambda )} \right]( - 1)^{n - (\mathop \Sigma \limits_{i = 1}^n x_i )} G[x_1 , x_2 , ..., x_n ]$$ where x=(x ₁,x ₂,…,x _n );G[k ₁,k ₂,…,k _n ] andP _n (γ) denote the characteristic polynomial ofG(k ₁,k ₂,…,k _n ) andP _n , respectively. Besides, ifG is a graph with λ₁(G)≥1 we show that λ₁(G)≤λ₁(G(k ₁,k ₂, ...,k _n )) < for all positive integersk ₁,k ₂,…,k _n , where λ₁ denotes the largest eigenvalue.     

On $\mathsf{c = 1}$ critical phases in anisotropic spin-1 chains

Quantum spin-1 chains may develop massless phases in presence of Ising-like and single-ion anisotropies. We have studied c = 1 critical phases by means of both analytical techniques, including a mapping of the lattice Hamiltonian onto an O(2) NL M, and a multi-target DMRG algorithm which allows for accurate calculation of excited states. We find excellent quantitative agreement with the theoretical predictions and conclude that a pure Gaussian model, without any orbifold construction, describes correctly the low-energy physics of these critical phases. This combined analysis indicates that the multicritical point at large single-ion anisotropy does not belong to the same universality class as the Takhtajan-Babujian Hamiltonian as claimed in the past. A link between string-order correlation functions and twisting vertex operators, along the c = 1 line that ends at this point, is also suggested.Received: 16 July 2003, Published online: 24 October 2003PACS: 75.40.-s Critical-point effects, specific heats, short-range order - 75.10.Jm Quantized spin models - 02.70.-c Computational techniques