Viewing the noise propagation mechanism in a unidirectional transition cascade from the perspective of stability

Noise and noise propagation are inevitable and play a constructive role in various biological processes. The stability of cell homeostasis is also a critical issue. In the unidirectional transition cascade of colon cells, stem cells (SCs) are the source. They differentiate into transit-amplifying cells (TACs), and TACs differentiate into fully differentiated cells (FDCs). Two differentiation processes are irreversible. The stability factor is introduced so that the noise propagation mechanism from the perspective of stability is studied according to the noise propagation formulas. It is found that the value of the stability factor corresponding to the minimum noise in FDCs may be the best choice to enable colon cells to maintain high stability and low noise of the cascade. Moreover, for the source cell, the total noise only includes intrinsic noise; for the downstream cell with self-proliferation capability, the total noise mainly depends on its intrinsic noise and transmitted noise from upstream cells, and its intrinsic noise is dominant. For the downstream cell without self-proliferation capability, the total noise is mainly determined by transmitted noises from upstream cells, and there is a minimum value. This work provides a new approach for studying the mechanism of noise propagation while considering the stability of cell homeostasis in biological systems.     

耐高温CrAlON基太阳能光谱选择性吸收涂层的制备与热稳定性

光谱选择性吸收涂层是太阳能光-热利用技术的核心部件,直接决定着整个系统的转换效率,为了提高涂层的选择吸收性和热稳定性,本文提出以金属氮化物替代金属纳米颗粒,构建纳米晶-非晶异质结构的思路,并采用多弧离子镀制备了Cr/CrAlN/CrAlON/CrAlN/CrAlON/CrAlO多吸收层光谱选择性吸收涂层,其吸收率达0.90,发射率为0.15,而且在500℃、大气条件下时效220 h后,涂层的吸收率升至0.94,发射率则降至0.10,并且能够保持稳定1000 h以上.微观组织分析表明,高温时效处理后,吸收层发生部分晶化形成了大量氮化物纳米颗粒,增加了对太阳光的散射和吸收,而CrAlO减反射层中的部分晶化形成了Al2O3和Cr2O3纳米颗粒,这不仅可以保护内部涂层不被氧化,而且Al2O3的形成可以增加太阳光的透过率,减少涂层表面反射,是多吸收层CrAlON基光谱选择性吸收涂层选择吸收性能提高的主要原因.同时,氮化物纳米颗粒被非晶基体均匀地分隔开来,形成了纳米晶-非晶异质结构,非晶在高温时效处理过程中只发生结构弛豫,从而有效地抑制了高温条件下的原子扩散,保证涂层中的纳米颗粒在高温下不发生明显团聚,这是多吸收层CrAlON基涂层具有良好热稳定性的最主要原因.这些研究结果对提高金属陶瓷光谱选择性吸收涂层的综合性能,实现更高效率的太阳能光-热利用具有重大意义.     

Cobalt(II) porphyrin axially coordinated with 2′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′-(pyridin-2-ylmethyl)-2′,4′-dihydro-1′H-pyrrolo[3′,4′ : 1,2](C60-Ih)[5,6]fullerene: formation,chemical structure,and spectroscopic properties

Construction of new effective photovoltaic devices based on organic dyes has important implications for modern and future technologies. In this article, we studied the equilibrium, the rate, and the spectral manifestation of the reaction of [(2,3,7,8,12,18-hexamethyl,13,17-diethyl,5-(2-pyridyl)porphyrinato)cobalt(II)]–[2′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′-(pyridin-2-ylmethyl)-2′,4′-dihydro-1′H-pyrrolo[3′,4′ : 1,2](C₆₀-I_h)[5,6]fullerene] triad formation as well as its spectral properties and photo electrochemical behavior. The cobalt porphyrin–pyridyl-substituted fullerene mixtures in toluene are self-assembling systems due to axial donor–acceptor binding between Co of the porphyrin complex and N-pyridyl of the substituted fullerene. The formation rate constant, k^298K, and the stability constant, K^298K, of donor–acceptor triad formed by coordination of two substituted fullerene molecules to Co porphyrin are (44.4 ± 0.8) mol L^?1 s^?1 and (56 ± 16)×10⁷ L² mol^?2, respectively. Modification of the titanium electrode coated with the natural oxide film was carried out using the porphyrin–fullerene triad and its individual components. Photopotential and photocurrent density of the system with modified electrode were studied. The obtained results are of interest for creating porphyrin-based donor–acceptor systems as components in organic photovoltaics.     

Toxic metal complexes of macrocyclic cyclen molecule – synthesis,structure and complexing properties

Toxic metal (Cd²⁺, Hg²⁺, Pb²⁺, and Ag⁺) complexes with the tetradentate macrocyclic ligand - cyclen (1,4,7,10-tetraazacyclododecane, [12]aneN₄, L) were prepared and studied in the solid state by IR, X-ray diffraction, elemental and thermal analysis. Diffraction results have yielded three molecular structures, [Cd([12]ane-κ⁴N^1,4,7,10)(NO₃)₂)] (1), [Hg([12]ane-κ⁴N^1,4,7,10)(NO₃-κ²O,O`)]NO₃ (2), [Pb₂([12]ane-κ⁴N^1,4,7,10)₂][Pb(NO₃)₆] (3) and one polymeric structure {[Ag₂([12]ane-κ³N^1,4,7)(μ₂-[12]aneN¹⁰)](NO₃)₂?2H₂O)}_n (4) featuring a unique coordination mode not observed before with cyclen as a ligand. The monodentate (1) and chelate (with small bite angle 50.3(3)°, (2) coordination modes of nitrate ligands were confirmed. Stereochemically active 6s² lone pair was suggested in 3 and DFT results confirmed no significant metal–metal covalent bond. The stability constants of the complexes with Cd²⁺ and Pb²⁺ ions were determined by potentiometric methods in aqueous solutions. Additionally, the structures of complexes in solution were observed by ¹H NMR. Both methods confirm similar cyclen complexing properties toward Zn²⁺ biometal and Cd²⁺, Pb²⁺ toxic metals.     

Construction of metal–organic frameworks from 3-(6-oxo-6,9-dihydro-1H-purin-1-yl)propionate

A series of metal–organic frameworks built from a propionate-functionalized purine-containing ligand 3-(6-oxo-6,9-dihydro-1H-purin-1-yl)propanoic acid (H₂L), {[La(HL)₃(H₂O)₂]·2H₂O}_n (1), {[Ce(HL)₃(H₂O)₂]·4H₂O}_n (2), [Co(HL)₂(H₂O)₂]_n (3), {[Cd(L)(H₂O)]·0.5H₂O}_n (4) and {[Pb(HL)(C₂O₄)_0.5(H₂O)]·2H₂O}_n (5), was synthesized and characterized. Isostructural 1 and 2 have polymeric chain structures further linked into 3-D porous supramolecular frameworks with 1-D open channels through complicated interchain hydrogen bonding interactions. At 77 K and 1 bar, the dehydrated porous materials 1 and 2 show adsorption behaviors with maximum nitrogen uptakes of 14 and 23 mL g^?1, respectively. Complexes 3–5 are 2-D coordination polymers but have different topological structures. Metallohelicate 3 has (4,4) nets composed of left- and right-handed metal–organic helices sharing the common metal centers, but metallohelicate 4 possesses (4·8²) topology and 5 has 6³-topological structure. In 3 and 5, the polymeric layers are further assembled through regular interlayer hydrogen bonding interactions to form 3-D supramolecular frameworks. Additionally, the thermostabilities of 1–5 as well as the magnetism of 3 were also investigated.     

Synthesis,characterization, speciation and biological studies on metal chelates of 1-benzoyl(1,2,4-triazol-3-yl)thiourea

Proton-ligand association constants of 1-benzoyl(1,2,4-triazol-3-yl)thiourea (BTTU) and its complex formation constants with some bivalent metal ions Ni(II), Co(II), Mn(II), Zn(II), and Cu(II), have been determined potentiometrically in 50% EtOH–H₂O and 0.1 M NaNO₃. The complexes formed in solution have a stoichiometry of 1:1 and 1:2 [M:L], where M represents the metal ion and L the BTTU ligand. The corresponding thermodynamic parameters are derived and discussed. The complexes are stabilized by enthalpy changes and the results suggest that complexation is an enthalpy-driven process. The effects of metal ion, ionic radius, electronegativity, and nature of ligand on the formation constants are discussed. The formation constants of the complexes with 3d transition metals follow the order Mn²⁺ < Co²⁺ < Ni²⁺ < Cu²⁺ > Zn²⁺. The metal complexes were synthesized and characterized by elemental analyses, conductance, IR, ¹H NMR, and magnetic measurements. The low magnetic moment of 0.11 BM for the Cu(II) complex is suggestive of dimerization through Cu–Cu interaction. The concentration distribution diagrams of the complexes were evaluated. The ligands and their metal complexes have been screened in vitro against some bacteria and fungi.     

The chemical bonding and spectral assignments of rhodium(III)‐catalyzed closo‐dodecaborate complexes: Ab initio study

The chemical bonding and spectral assignments of rhodium(III)‐catalyzed closo‐dodecaborate (RhCD) complex are systematically studied using the density functional theory calculations. It is found that the calculated main bond lengths of framework are in good agreement with experimental X‐ray observation, and the pronounced hybridization of B‐2p and Rh‐4d states is responsible for the structural stability, reflected by the large dissociation energy and HOMO–LUMO energy gap. The AdNDP chemical bonding analysis indicates that the RhCD complex can be stabilized by two H‐bridged 3c‐2e σ‐bonds (B‐H‐Rh triangles). Additionally, the theoretical calculations reproduce well the main experimental IR spectrum, and the characteristic peaks are properly assigned. These results will be helpful for further insight into the unique electronic structure of the species, and provide valuable references for potential applications in novel materials.     

In situ PM‐IRRAS studies of organothiols and organosilane monolayers–ZnO interfaces at high water activities

In situ photoelastic‐modulated Fourier transform infrared reflection absorption spectroscopy has been applied for the investigation of interfacial stability of organothiol and organosilane monolayer films on nanocrystalline zinc oxide thin films. It has been shown that for octadecyltriethoxysilane films, exposure to high water activities results in physisorption of water in the cross‐linked film. This high water activity at the interface leads to a reversible wet de‐adhesion of the interfacial silanol groups from the ZnO surface. However, the organothiol seems to form a denser monolayer and a stable by S–Zn bond that is resistant to the competition with adsorbed water. The reversible attachment for cross‐linked organosilanol films has been demonstrated for the first time by means of an in situ spectroscopic method on model ZnO surfaces. Copyright © 2016 John Wiley & Sons, Ltd.     

Effect of liquid oils on the properties of multiple emulsions containing liquid crystals

Recently, many cosmetic researchers have been focused on multiple emulsions due to better performance. Limited application of multiple emulsions has been attributed to their instability, which can be resolved by the presence of liquid crystals. Multiple emulsions containing liquid crystals are affected by various formulation parameters, such as liquid oils. In this paper, the influence of liquid oils on the formation mechanism was studied. Besides, stability, small-angle x-ray scattering (SAXS) spectra analysis, and rheological analysis of the emulsions were investigated as well. The results showed that when the gap of the polarity between inner oils and external liquid oils is greater, the multiple structures were more easily formed. Multiple emulsions containing liquid crystals were superior in stability to multiple emulsions prepared in the same way with liquid oils that did not form liquid crystals. SAXS indicated that the liquid crystal orientation was lamellar. Rheological analysis indicated that the different structure emulsions showed shear-thinning behavior. The presence of liquid crystal decreased the viscosity and resulted in pseudoplastic enhancement. Both the storage modulus (G′) and the loss modulus (G″) of multiple emulsions were slightly higher than those of O/W-type emulsions, implying the existence of multiple structures.     

铝-锂合金动态扭转实验研究

利用霍普金森扭杆（Torsional Split-Hopkinson Bar）技术对三种不同成份或状态的铝-锂合金材料的动态应力-应变-应变率关系进行了实验测定。应变率范围由1300s-1到2600s-1,研究表明随着应变率的提高,三种不同成份或状态的铝-锂合金材料的韧性和强度都有不同程度的提高。对剪切带的初步观察发现,随应变率的增加,剪切带有变窄的趋势。