A protein-polymer hybrid mediated by DNA

Protein-polymer hybrids (PPHs) represent an important and rapidly expanding class of biomaterials. Typically in these hybrids the linkage between the protein and the polymer is covalent. Here we describe a straightforward approach to a noncovalent PPH that is mediated by DNA. Although noncovalent, the DNA-mediated approach affords the highly specific pairing and assembly properties of DNA. To obtain the protein-DNA conjugate for assembly of the PPH, we report here the first direct copper catalyzed azide-alkyne cycloaddition-based protein-DNA conjugation. This significantly simplifies access to protein-DNA conjugates. The protein-DNA conjugate and partner polymer-DNA conjugate are readily assembled through annealing of the cDNA strands to obtain the PPH, the assembly of which was confirmed via dynamic light scattering and fluorescence spectroscopy.     

Unusual nitro-coordination of europium(iii) and terbium(iii) with pyridinyl ligands

A new ligand family based on picoline, bipyridine and terpyridine containing a nitro moiety has been synthesized and its coordination and sensitization ability for lanthanide ions has been studied. Three new complexes were characterized by X-ray single crystal diffraction and all three show uncommon coordination of the nitro moiety to the lanthanide ion. , a terpyridine-nitro derivative with Tb(NO(3))(3), crystallizes in the orthorhombic space group Pbca with a = 15.125(3), b = 13.776(3), c = 18.716(4) ?, and V = 3899.8(13) ?(3) and is isostructural with its Eu(iii) analog () with cell parameters a = 15.1341(4), b = 13.7070(4), c = 18.8277(5) ?. , a tripodal amine with a nitro-derivatized pyridine with Eu(CF(3)SO(3))(3), crystallizes in the triclinic space group P1[combining macron] with a = 11.067(2), b = 11.633(2), c = 12.772(3) ?, α = 110.94(3), β = 97.49(3), γ = 91.42(3)° and V = 1518.1(5) ?(3). Finally, ligand , a bipyridine-nitro derivative, crystallizes in the orthorhombic space group P2(1)/n with a = 3.7128(3), b = 11.7806(8), c = 19.9856(14) ?, β = 92.925(2)° and V = 873.01(11) ?(3). All four ligands show sensitization of Eu(iii) and Tb(iii) luminescence.     

Analyzing coordination preferences of Mg2+ complexes: insights from computational and database study

Solvation of metal cations has attracted substantial interest on account of its functional importance in biological systems. In the present study, we undertake a comprehensive analysis of hydrated complexes of Mg²⁺ with up to 20 water molecules using MP2/cc-pVTZ and density functional theory (DFT) calculations. The effect of first, second, and higher solvation shells on magnesium coordination has been systematically analyzed by considering Mg²⁺(H₂O) _n complexes. Numerous competing conformations for each of the metal ion complexes have been explored and the minima structures obtained were further analyzed. The study probes the relative preferences among various coordination numbers and unambiguously establishes that coordination number 6 is the most optimal choice. The relative abundance of Mg²⁺ ion and its coordination with water and other ligands has been analyzed in the Protein Data Bank and Cambridge Structural Database. It is noted that the M–O distance and charge transfer to metal ion increase as the number of solvating water molecules increases. The computational studies are in excellent agreement with the experimental observations, and provide support to multiple coordinate site preferences for Mg²⁺.     

A first principles molecular dynamics study of excess electron and lithium atom solvation in water-ammonia mixed clusters: structural, spectral, and dynamical behaviors of [(H2O)5NH3]- and Li(H2O)5NH3 at finite temperature

First principles molecular dynamics simulations are carried out to investigate the solvation of an excess electron and a lithium atom in mixed water-ammonia cluster (H(2)O)(5)NH(3) at a finite temperature of 150 K. Both [(H(2)O)(5)NH(3)](-) and Li(H(2)O)(5)NH(3) clusters are seen to display substantial hydrogen bond dynamics due to thermal motion leading to many different isomeric structures. Also, the structures of these two clusters are found to be very different from each other and also very different from the corresponding neutral cluster without any excess electron or the metal atom. Spontaneous ionization of Li atom occurs in the case of Li(H(2)O)(5)NH(3). The spatial distribution of the singly occupied molecular orbital shows where and how the excess (or free) electron is primarily localized in these clusters. The populations of single acceptor (A), double acceptor (AA), and free (NIL) type water and ammonia molecules are found to be significantly high. The dangling hydrogens of these type of water or ammonia molecules are found to primarily capture the free electron. It is also found that the free electron binding motifs evolve with time due to thermal fluctuations and the vertical detachment energy of [(H(2)O)(5)NH(3)](-) and vertical ionization energy of Li(H(2)O)(5)NH(3) also change with time along the simulation trajectories. Assignments of the observed peaks in the vibrational power spectra are done and we found a one to one correlation between the time-averaged populations of water and ammonia molecules at different H-bonding sites with the various peaks of power spectra. The frequency-time correlation functions of OH stretch vibrational frequencies of these clusters are also calculated and their decay profiles are analyzed in terms of the dynamics of hydrogen bonded and dangling OH modes. It is found that the hydrogen bond lifetimes in these clusters are almost five to six times longer than that of pure liquid water at room temperature.     

Holographic Image Denoising using Random Laser Illumination

In holographic applications, coherent lasers are indispensable source of illumination. Despite high intensity from coherent light sources, they fail in full-field image projection and illustrate speckle images due to high spatial coherence. This article demonstrates speckle-free high contrast computer-generated holographic image projection upon illumination with a perovskite–polystyrene 10 wt%-based random laser. Solvent-engineered efficient and durable perovskite and perovskite–polystyrene 10 wt%-based random lasers are fabricated. Optical characterizations are elucidated and controlled coherence random lasing operation is achieved under room temperature upon addition of polystyrene concentration 10 wt% on perovskite thin film. The addition of 10 wt% polystyrene concentration results in a low far-field divergence angle of ≈10⁰. The controlled coherence in random lasers is necessary to produce a stable interference pattern and to retain the depth of field in holograms. Additionally, the holographic image projection using random lasers reduces diffraction noise, and exhibits high spatial resolution with full-field imaging. Moreover, this study is clear evidence of an effective strategy to achieve high-performance, indigenous designed-controlled coherence in disordered random lasing media and its application to novel holographic image projection.     

Interaction of Amino Acid Schiff Base Metal Complexes with DNA/BSA Protein and Antibacterial Activity: Spectral Studies,DFT Calculations and Molecular Docking Simulations

Cu(II), Ni(II) and Zn(II) complexes of (E)‐2‐((2,4‐dihydroxybenzylidene)amino)‐3‐(1H‐indol‐3‐yl)propanoic acid Schiff base ( L ) were synthesized and characterized by various spectral methods. ESI‐MS was used to confirm the structure of synthesized compounds. Molecular geometries of the complexes were predicted by optimizing the structure by DFT/B3LYP method with LANL2DZ basis set in the gas phase. The interaction of the metal complexes with CT‐DNA and BSA protein has been examined by UV‐vis, fluorescence and viscometer titrations reveal that the complexes bind to DNA through intercalation binding mode. The copper complexes exhibit effective cleavage of pUC19 DNA by the oxidative mechanism. The synthesized compounds screened for their antibacterial activities against various bacteria strains exhibit the L and copper complex show potential activity against Pseudomonas aeruginosa and Escherichia coli, respectively. Subsequently, molecular docking studies were performed on to understand the binding of the compounds with DNA, BSA and bacteria.     

Thermohaline convection with finite amplitude in a rotating fluid

Zusammenfassung Die Stabilitätseigenschaft einer von unten erwärmten, unendlich ausgedehnten, horizontalen Flüssigkeitsschicht wird untersucht in dem Fall, wenn ein stabilisierender Salz-Konzentrations-gradient gegeben ist und die Flüssigkeitsschicht mit konstanter Winkelgeschwindigkeit um eine vertikale Achse rotiert. Die Untersuchung infinitesimaler Störungen zeigt, dass das System zuerst gegenüber oszillierenden Störungen instabil wird. Darüber hinaus wird an dem Beispiel von Strömungen in der Form von Rollen gezeigt, dass die Schicht gegenüber Störungen endlicher Amplitude instabil wird, bevor infinitesimale Störungen anwachsen. Die Rotation übt eine stabilisierende Wirkung aus. Der Einfluss von Rotation und Salz-Konzentrationsgradient auf den Wärmetransport wird diskutiert.     

Structural analysis of arylsulfonamide-based carboxylic acid derivatives: a QSAR study to identify the structural contributors toward their MMP-9 inhibition

Structural Chemistry - Matrix metalloproteinases (MMPs) are a group of endopeptidases renowned for their ability to degrade the extracellular matrix (ECM) and contribute in different physiological...     

Nitro-functionalization and luminescence quantum yield of Eu(III) and Tb(III) benzoic acid complexes

In our pursuit of luminescent lanthanide ion-based coordination polymers, we have isolated several complexes with nitrobenzoic acid ligands and characterized these by X-ray crystallography and luminescence spectroscopy. 2-Nitrobenzoic acid reacts with Eu(III) to form 1, which crystallizes in the P-1 space group, with a = 12.385(3), b = 12.912(3), c = 17.889(4) A, alpha = 97.49(3), beta = 109.64(3) and gamma = 101.99(3) degrees . 3-Nitrobenzoic acid forms a one-dimensional coordination polymer with Eu(III), 2, which crystallizes in the triclinic space group P-1 with a = 9.7100(19), b = 10.579(2), c = 13.361(3) A, alpha = 77.41(3), beta = 88.78(3) and gamma = 88.16(3) degrees. Structures 3 and 4 correspond to the isostructural one-dimensional coordination polymers of Eu(III) and Tb(III), respectively, with the 4-nitrobenzoato anion. These crystallize in the triclinic space group P-1 with a = 9.2242(18), b = 15.102(3), c = 18.587(4) A, alpha = 75.93(3), beta = 82.88(3) and gamma = 79.00(3) degrees for 3 and a = 9.2692(19), b = 15.369(3), c = 18.353(4) A, alpha = 75.37(3), beta = 81.32(3) and gamma = 78.15(3) degrees for 4. Potentiometry, absorption and NMR spectroscopy indicate that in solution only 1 : 1 species are present. All compounds are weakly luminescent as solids and the photophysics of solutions of ligands with Ln(III) in 1 : 1 stoichiometry were studied. Quantum yields around 1 and 3% for Eu(III)-and Tb(III)-containing methanolic solutions were measured.