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991.
Florian P. Weissenboeck Helena Schepers Prof. Dr. Andrea Rentmeister 《Angewandte Chemie (International ed. in English)》2023,62(23):e202301778
A major stage in the expression of genes is the translation of messenger RNA (mRNA), and the regulation of this process is essential for protein production in cells. How tightly controlled gene expression can be spatially and temporally, is particularly evident in polar cells and embryonic development. We need tools to dissect these complex processes, if we wish to understand the underlying links, especially the difficulties brought on by malfunction. External bioorthogonal triggers are very helpful in this area, if they let us precisely control where and when a process is started. Equipping nucleic acids with light-responsive groups has proven to be an effective approach to examine the dynamic regulatory route of mRNA translation in living cells. In this review, we present an overview of the most recent methods for optochemically controlling translation, focusing on cis-acting technologies. 相似文献
992.
Dr. Wenhui Niu Dr. Yubin Fu Gianluca Serra Kun Liu Jörn Droste Yeonju Lee Zhitian Ling Dr. Fugui Xu Dr. José D. Cojal González Dr. Andrea Lucotti Prof. Dr. Jürgen P. Rabe Prof. Dr. Michael Ryan Hansen Prof. Dr. Wojciech Pisula Prof. Dr. Paul W. M. Blom Prof. Dr. Carlos-Andres Palma Prof. Dr. Matteo Tommasini Prof. Dr. Yiyong Mai Dr. Ji Ma Prof. Dr. Xinliang Feng 《Angewandte Chemie (International ed. in English)》2023,62(35):e202305737
The incorporation of nanopores into graphene nanostructures has been demonstrated as an efficient tool in tuning their band gaps and electronic structures. However, precisely embedding the uniform nanopores into graphene nanoribbons (GNRs) at the atomic level remains underdeveloped especially for in-solution synthesis due to the lack of efficient synthetic strategies. Herein we report the first case of solution-synthesized porous GNR ( pGNR ) with a fully conjugated backbone via the efficient Scholl reaction of tailor-made polyphenylene precursor ( P1 ) bearing pre-installed hexagonal nanopores. The resultant pGNR features periodic subnanometer pores with a uniform diameter of 0.6 nm and an adjacent-pores-distance of 1.7 nm. To solidify our design strategy, two porous model compounds ( 1 a , 1 b ) containing the same pore size as the shortcuts of pGNR , are successfully synthesized. The chemical structure and photophysical properties of pGNR are investigated by various spectroscopic analyses. Notably, the embedded periodic nanopores largely reduce the π-conjugation degree and alleviate the inter-ribbon π–π interactions, compared to the nonporous GNRs with similar widths, affording pGNR with a notably enlarged band gap and enhanced liquid-phase processability. 相似文献
993.
Andrea Kagie Daniel K. Bishop Jared Burdick Jeffrey T. La Belle Robert Dymond Robin Felder Joseph Wang 《Electroanalysis》2008,20(14):1610-1614
We describe here a miniaturized flexible thick‐film electrochemical biosensor flow detector, suitable for insertion into the lacrimal canaliculus towards minimally invasive amperometric monitoring of biomarkers in the tear fluid. Our focus here is on the microfabrication and in‐vitro testing of the new laterally rolled screen‐printed sensor. The new device responds rapidly and sensitively to dynamic changes in the levels of norepinephrine and glucose (the later in connection to glucose‐oxidase containing ink). Coverage of the enzyme electrode with an electropolymerized polytyramine minimizes contributions from the common electroactive interferences ascorbic and uric acids. Such attractive performance indicates great promise for minimally invasive monitoring of health biomarkers in the tear fluid, or in alternative usage such as capillary microelectrophoresis, ultralow volume sampling, or in‐flow (tubular) systems for batch processing of blood or culture media. 相似文献
994.
Ernesto Schulz Lang Gelson Manzoni de Oliveira Bárbara Tirloni Marcos Antonio Villetti 《Journal of Cluster Science》2008,19(3):459-469
(PhTe)2Hg reacts with HgCl2 and triphenylphosphine to give the clusters [(PhTe)6(Ph3P)2Hg5Cl4] · 2THF (1) and [(PhTe)8Hg6Py2Cl4] · Py (Py = pyridine) (2). In 1 each tellurium atom connects two Hg atoms, with Hg–Te distances around 2.75 Å. Phosphorus atoms of the triphenylphosphine groups complete the tetrahedral coordination of the Hg1 atoms. The second set
of Hg atoms (Hg2) is also coordinated to chlorine atoms. The three-dimensional assembling of 1 encloses circular channels with medium diameter of 12.5 Å. The cluster 2 results from substitution of the oxidized triphenylphosphine ligands of 1 by one molecule of Hg(PhTe)2 in the course of the synthetic procedures. The alternated Te–Hg bonds of 2 close a 12-membered ring with two inverted 4-membered rings in the middle. Thermogravimetrical evaluations and Raman scattering
lines of 1 and 2 are also discussed.
相似文献
Gelson Manzoni de Oliveira (Corresponding author)Email: |
995.
Picolinamide (PA) and isonicotinamide (INA), two structural isomers of pyridinecarboxamide, have been investigated by matrix isolation and low-temperature solid-state infrared spectroscopy, combined with UV (lambda > 235 nm) photoexcitation and density functional theory and ab initio (MP2) theoretical studies. In consonance with the theoretical data, both PA and INA were found to exist in a single conformation in cryogenic rare gas matrixes. Comparison between the experimental spectra of the matrix-isolated compounds with those theoretically predicted allowed for full assignment of the experimental spectra. In situ UV (lambda > 235 nm) irradiation of the matrixes showed that only PA reacts, with production of isocyanic acid and pyridine, the first photoproduct further reacting to yield CO + NH and cyanic acid. The different photochemical behavior of the two compounds was explained taking into consideration their different structures. The infrared spectra of (i) the low-temperature glassy state resulting from fast deposition of vapors of the compounds onto a substrate cooled to 10 K, (ii) the crystal resulting from the annealed amorphous film of the compound, and (iii) the room-temperature crystals (alpha-phase) of the studied compounds were also obtained, fully assigned and correlated with intermolecular interactions present in the condensed phases, in particular H-bond interactions, showing that these latter are stronger in INA than in PA. 相似文献
996.
Callierotti G Bianco A Castiglioni C Bertarelli C Zerbi G 《The journal of physical chemistry. A》2008,112(32):7473-7480
Molecular polarizabilities of photochromic diarylethenes bearing different chemical groups as substituents have been calculated by density functional theory (DFT) simulations with the aim to obtain an estimate of the refractive index of a glassy matrix containing diarylethenes as active species. Simple models have been introduced in order to take into account the effects that occur in bulk materials. The results obtained show that the choice of suitable substituents enhances the modulation of the refractive index driven by the photochromic reaction; moreover, the trends predicted are consistent with the experimental data. This opens the way to use quantum chemical predictions on model molecules to foresee performances relative to the photoinduced modulation of the refractive index in bulk materials. 相似文献
997.
Gómez-Zavaglia A Kaczor A Almeida R Cristiano Mde L Fausto R 《The journal of physical chemistry. A》2008,112(8):1762-1772
In this work, the conformational space of the pseudosaccharyl ether 3-(allyloxy)-1,2-benzisothiazole 1,1-dioxide (ABID) has been studied by means of infrared spectroscopy and density functional theory (DFT) calculations. Five different low energy conformers (TSk, TC, GSk, GSk' and GC, with relative energies of 0.00, 1.97, 2.00, 3.82 and 6.02 kJ mol(-1), respectively) were found on the DFT(B3LYP)/6-311++G(3df,3pd) potential energy surface of the molecule, all of them differing in the conformation of the allyl substituent. According to the calculations, in the gaseous phase all conformers are significantly populated (TSk:TC:GSk:GSk':GC = 47%:16%:18%:12%:7%, at 350 K). In the cryogenic matrices, however, only the TSk and TC conformers exist due to isomerization from the higher energy gauche forms to the most stable trans isomers during deposition of the matrix (conformational cooling). The observed conformational cooling is in consonance with the low calculated energy barriers for the GSk --> TSk, GSk' --> TSk and GC --> TC isomerization processes. Results from annealing experiments in krypton matrix doubtlessly show that in this matrix the order of stability of the TSk and TC conformers is reversed, with the more planar TC form becoming the most stable conformer. 相似文献
998.
Since secondary structure elements are known to play a key role in stabilizing the 3D-fold of proteins for the design of non-natural proteins composed of beta-amino acid residues, the construction of suitable secondary structural elements is mandatory. Folding analogues of alpha-helices and beta-strands of beta-polypeptides were already described (Chem. Biodiversity 2004, 1, 1111 (1)). Here, we present several collagen-like folds composed exclusively of beta-Ala(s). Unlike their natural counterpart, these tubular nanostructures can be composed of more than three polypeptide chains aligned parallel and/or antiparallel. By using ab initio and DFT calculations we have optimized a large number of versatile collagen-like antiparallel nanostructures. In these tubular systems, oligopeptide strands are interconnected by i --> (i) type H-bonds, except for the "closing" set. This latter is called "the H-bond zipper" and is either (i) --> i, ( i + 1) --> i, or ( i + 2) --> i type. Antiparallel, tubular foldamers composed of l number of strands, each of k number of beta-amino acid residues (e.g., apbeta-T(l) i+l ) k , ap(beta-T(l) i+1 ) k , or ap(beta-T(l) i+2 ) k ), are unexpectedly stable supramolecular complexes. Independent of k and l, the local backbone fold of the amino acid residues is usually spiral, abbreviated as "S(P)" or "S*(P)". Nevertheless, in contrast to parallel, in antiparallel nanotubes the backbone fold can occasionally twist out from S(P) or S*(P) type into an alternative local structure. However, the more the local geometry of the strands resembles to S(P) or S*(P), the higher the stability is. Besides the backbone twisting, the overall stability is determined by the type and the geometrical properties of the constituent H-bonds. Interestingly, higher number of total H-bonds can provide a lower overall stability, when H-bond parameters are inferior. In general, the increase of both the number of strands and their length stabilize the supramolecular complex. Now that, for beta-peptides, collagen-like overall folds with their stability were determined, their POG- or PPG-like sequence specificity has to be revealed. 相似文献
999.
We show that the complementary error function, $\text{erfc} (z)= \frac{2}{\sqrt{\pi}}\int_z^{\infty}{e^{-s^2} \text{d}s}$ , has no zeros in $\text{D}= \left\{ z : \frac{3}{4} \ \pi \le Arg z \le\frac{5}{4} \ \pi \right\}$ . 相似文献
1000.
Andrea Bettinelli Alberto Ceselli Giovanni Righini 《4OR: A Quarterly Journal of Operations Research》2008,6(4):361-374
The two-dimensional level strip packing problem (2LSPP) consists in packing rectangular items of given size into a strip of
given width divided into levels. Items packed into the same level cannot be put on top of one another and their overall width
cannot exceed the width of the strip. The objective is to accommodate all the items while minimizing the overall height of
the strip. The problem is -hard and arises from applications in logistics and transportation. We present a set covering formulation of the 2LSPP suitable
for a column generation approach, where each column corresponds to a feasible combination of items inserted into the same
level. For the exact optimization of the 2LSPP we present a branch-and-price algorithm, in which the pricing problem is a
penalized knapsack problem. Computational results are reported for benchmark instances with some hundreds items. 相似文献