Three dimension Liesegang rings of calcium hydrophosphate in gelatin

Three dimensional Liesegang spherical layers of CaHPO₄ in gelatin ball were performed by employing CaCl₂ and Na₂HPO₄ as the inner and outer electrolyte, respectively. Effects of concentrations of inner and outer electrolyte as well as pH on the morphologies of Liesegang rings (LRs) were investigated. As a result, it was observed that the time law, spacing law and width law found in 1D/2D gel systems were obeyed in this 3D gelatin system. The interaction of Ca²⁺ and HPO₄ ^2? with gelatin matrix played a key role to the formation of LRs due to the existence of carboxylic groups on the gelatin chains. Using Ca²⁺ as the inner electrolyte, LRs were prepared. However, employing HPO₄ ^2? as inner electrolyte, LRs were not obtained. Moreover, pH of gelatin solution greatly impacted on the formation of LRs. The number of LRs increased with the decrease of pH, whereas the width inversely decreased. pH 4.40 was a turn point, from which the spacing coefficient abruptly increased as pH increased. All these results indicated that the network was created by the interaction of Ca²⁺ and –COO^? of gelatin chains, which dominated the formation of CaHPO₄ LRs in gelatin.     

The oxygen sensitive properties of (LaBa)Co2O5+δ thin films fabricated by polymer-assisted deposition technique

(LaBa)Co₂O_5+δ (LBCO) thin films were successfully fabricated on Si (001) substrates by polymer-assisted deposition method. Microstructures were examined by X-ray diffraction technique, which confirmed the films were a single phase, pseudo cubic structure. The electrical transport properties of the films were investigated by the temperature dependence of films resistance, which suggested that LBCO films have typical semiconductor properties. After circle tests, the oxygen–hydrogen response rate did not show obvious variation in the specific temperature environment of 580 °C. This demonstrates that the LBCO thin films have a superior stability in both oxygen and hydrogen (6 % H₂, 94 % N₂) environment. Simultaneously, the drastic changes of films resistance (from ~10⁶ to ~10² Ω) with the switch of redox (O₂–H₂) environment within such a short time (~2.2 s) indicated that LBCO films have an excellent oxygen sensitive property and extraordinary fast surface exchange rate.     

聚L-谷氨酸苄酯固定相的制备及色谱评价

利用L-谷氨酸苄酯开环聚合得到聚L-谷氨酸苄酯,对其进行表征,将聚L-谷氨酸苄酯溶于四氢呋喃后涂敷在3-氨丙基三乙氧基硅胶上制得液相色谱固定相,研究了正相色谱条件下聚L-谷氨酸苄酯涂敷型固定相对9种位置异构体及10种手性化合物的拆分能力。以不同比例的正己烷/异丙醇为流动相,有6种位置异构体(o,m,p-氯苯胺、o,m,p-溴苯胺、o,m,p-碘苯胺、o,m,p-硝基苯胺、o,m,p-二硝基苯和o,m,p-苯二胺)和4种手性化合物(1-(对氯苯基)乙醇、5-二硝基-N-(1-苯乙基)苯甲酰胺、华法林和四咪唑)得到不同程度的拆分,表明聚L-谷氨酸苄酯涂敷型固定相对位置异构体具有较好的识别作用,同时也表现出良好的手性拆分能力。     

A Hydrogen-Deficient Nickel–Cobalt Double Hydroxide for Photocatalytic Overall Water Splitting

Developing highly efficient and low-cost photocatalysts for overall water splitting has long been a pursuit for converting solar power into clean hydrogen energy. Herein, we demonstrate that a nonstoichiometric nickel–cobalt double hydroxide can achieve overall water splitting by itself upon solar light irradiation, avoiding the consumption of noble-metal co-catalysts. We employed an intensive laser to ablate a NiCo alloy target immersed in alkaline solution, and produced so-called L-NiCo nanosheets with a nonstoichiometric composition and O²⁻/Co³⁺ ions exposed on the surface. The nonstoichiometric composition broadens the band gap, while O²⁻ and Co³⁺ ions boost hydrogen and oxygen evolution, respectively. As such, the photocatalyst achieves a H₂ evolution rate of 1.7 μmol h⁻¹ under AM 1.5G sunlight irradiation and an apparent quantum yield (AQE) of 1.38 % at 380 nm.     

π-Interactions between Cyclic Carbocations and Aromatics Cause Zeolite Deactivation in Methanol-to-Hydrocarbon Conversion

The understanding of catalyst deactivation represents one of the major challenges for the methanol-to-hydrocarbon (MTH) reaction over acidic zeolites. Here we report the critical role of intermolecular π-interactions in catalyst deactivation in the MTH reaction on zeolites H-SSZ-13 and H-ZSM-5. π-interaction-induced spatial proximities between cyclopentenyl cations and aromatics in the confined channels and/or cages of zeolites are revealed by two-dimensional solid-state NMR spectroscopy. The formation of naphtalene as a precursor to coke species is favored due to the reaction of aromatics with the nearby cyclopentenyl cations and correlates with both acid density and zeolite topology.     

Water-Insensitive Synthesis of Poly-β-Peptides with Defined Architecture

Biocompatible and proteolysis-resistant poly-β-peptides have broad applications and are dominantly synthesized via the harsh and water-sensitive ring-opening polymerization of β-lactams in a glovebox or using a Schlenk line, catalyzed by the strong base LiN(SiMe₃)₂. We have developed a controllable and water-insensitive ring-opening polymerization of β-amino acid N-thiocarboxyanhydrides (β-NTAs) that can be operated in open vessels to prepare poly-β-peptides in high yields, with diverse functional groups, variable chain length, narrow dispersity and defined architecture. These merits imply wide applications of β-NTA polymerization and resulting poly-β-peptides, which is validated by the finding of a HDP-mimicking poly-β-peptide with potent antimicrobial activities. The living β-NTA polymerization enables the controllable synthesis of random, block copolymers and easy tuning of both terminal groups of polypeptides, which facilitated the unravelling of the antibacterial mechanism using the fluorophore-labelled poly-β-peptide.     

Monochromophore-Based Phosphorescence and Fluorescence from Pure Organic Assemblies for Ratiometric Hypoxia Detection

Hypoxia is a parameter related to many diseases. Ratiometric hypoxia probes often rely on a combination of an O₂-insensitive fluorophore and an O₂-sensitive phosphor in a polymer matrix, which require high cost and multi-step synthesis of transition metal complexes. The two-chromophore hypoxia probes encounter unfavorable energy transfer processes and different stabilities of the chromophores. Reported herein is a pure organic ratiometric hypoxia nanoprobe, assembled by a monochromophore, naphthalimide ureidopyrimidinone (BrNpA-UPy), bridged by a bis-UPy-functionalized benzyl skeleton. The joint factors of quadruple hydrogen bonding, the rigid backbone of UPy, and bromine substitution of the naphthalimide derivative facilitate bright phosphorescence (Φ_P=7.7 %, τ_P=3.2 ms) and fluorescence of the resultant nanoparticles (SNPs) at room temperature, which enable accurate, ratiometric, sensitive oxygen detection (K_sv=189.6 kPa⁻¹) in aqueous solution as well as in living HeLa cells.     

Rational Design of the Metal-Free KBe2BO3F2⋅(KBBF) Family Member C(NH2)3SO3F with Ultraviolet Optical Nonlinearity

The first fluorosulfonic ultraviolet (UV) nonlinear optical (NLO) material, C(NH₂)₃SO₃F, is rationally designed by taking KBe₂BO₃F₂ (KBBF) as the parent compound. C(NH₂)₃SO₃F features similar topological layers as KBBF by replacing inorganic (BO₃)³⁻ with organic C(NH₂)₃⁺ trigonal units and BeO₃F with SO₃F⁻ tetrahedra. Therefore, C(NH₂)₃SO₃F is a metal-free UV NLO crystal. Benefiting from the coplanar configuration of the C(NH₂)₃⁺ cationic groups, it possesses a large SHG response of 5×KDP and moderate birefringence of 0.133@1064 nm. Besides, it has a short UV cutoff edge of 200 nm. The calculated results reveal the shortest SHG phase-matching wavelengths can reach 200 nm. These findings highlight the exploration of metal-free compounds as nontoxic and low-cost UV NLO materials as a new research area.     

Ordered Large-Pore MesoMOFs Based on Synergistic Effects of TriBlock Polymer and Hofmeister Ion

Ordered mesoporous metal–organic frameworks (mesoMOFs) were constructed with a uniform pore size up to about 10 nm and thick microporous walls, opening up the possibility for the mass diffusion of large-size molecules through crystalline MOFs. The synergistic effects based on triblock copolymer templates and the Hofmeister salting-in anions promote the nucleation of stable MOFs in aqueous phase and the in situ crystallization of MOFs around templates, rendering the generation of a microcrystal with periodically arranged large mesopores. The improved mass transfer benefiting from large-pore channels, together with robust microporous crystalline structure, endows them as an ideal nanoreactor for the highly efficient digestion of various biogenic proteins. This strategy could set a guideline for the rational design of new ordered large-pore mesoMOFs with a variety of compositions and functionalities and pave a way for their potential applications with biomacromolecules.     

Research on gamma-ray irradiation-assisted synthesis of cross-linked polystyrene via bulk polymerization

Journal of Radioanalytical and Nuclear Chemistry - Controlling heat accumulation is one of the major challenges for block materials synthesizing via bulk polymerization. In the paper, cross-linked...