Time‐Resolved Energetics of Photoprocesses in Prokaryotic Phytochrome‐Related Photoreceptors

Time‐resolved photoacoustics (PA) is uniquely able to explore the energy landscape of photoactive proteins and concomitantly detects light‐induced volumetric changes (ΔV) accompanying the formation and decay of transient species in a time window between ca. 20 ns and 5 μs. Here, we report PA measurements on diverse photochromic bilin‐binding photoreceptors of prokaryotic origin: (1) the chromophore‐binding GAF3 domain of the red (R)/green (G) switching cyanobacteriochrome 1393 (Slr1393g3) from Synechocystis; (2) the red/far red (R/FR) Synechocystis Cph1 phytochrome; (3) full‐length and truncated constructs of Xanthomonas campestris bacteriophytochrome (XccBphP), absorbing up to the NIR spectral region. In almost all cases, photoisomerization results in a large fraction of energy dissipated as heat (up to 90%) on the sub‐ns scale, reflecting the low photoisomerization quantum yield (<0.2). This “prompt” step is accompanied by a positive ΔV₁ = 5–12.5 mL mol^?1. Formation of the first intermediate is the sole process accessible to PA, with the notable exception of Slr1393g3‐G for which ΔV₁ = +4.5 mL mol^?1 is followed by a time‐resolved, energy‐conserving contraction ΔV₂ = ?11.4 mL mol^?1, τ₂ = 180 ns at 2.4°C. This peculiarity is possibly due to a larger solvent occupancy of the chromophore cavity for Slr1393g3‐G.     

Ring-contraction from benzo[b][1,4]thiazines to benzo[d]thiazolines induced by oxygen

An unexpected ring-contraction from benzo[b]pyrazino[1,2-d][1,4]thiazine-1,4-diones (6) to benzo[4,5]thiazolo[3,2-a]pyrazine-1,4-diones (7) has been developed. The preliminary mechanistic studies showed the transformation contained two independent steps: the first step is the formation of a Michael adduct upon the addition of the protic solvent, in the presence of base, to the C-2-C-3 double bond of compound 6, and the second step is a ring-contraction induced by oxygen via the migration of sulfur atom from C-2 to C-3 position. And its scope is also studied.     

Nanographite-based fluorescent biosensing of Salmonella enteritidis by applying deoxyribonuclease-assisted recycling

Microchimica Acta - The authors describe a low-cost and sensitive method for the fluorometric determination of Salmonella enteritidis (S. enteritidis). It is based on the use of nanographite (NG)...     

Palladium nanoparticles stabilized by phosphine ligand for aqueous phase room temperature suzuki-Miyaura coupling

Water soluble phosphine ligand triphenylphosphine-3,3′,3″-trisulfonic acid trisodium salt (TPPTS) was used as the stabilizer as well as the activator to the palladium nanoparticles, which showed a high catalytic performance for aqueous phase Suzuki-Miyaura coupling reaction at room temperature.     

Novel simple fluorescent sensor for nickel ions

A novel pyrazoline with benzimidazole substituent was conveniently synthesized, starting from a chalcone and 2-hydrazinylpyridine. The addition of Ni²⁺ to ethanol solution of the synthesized pyrazoline resulted in a rapid color change from blue to green which allows the selective detection of Ni²⁺ ion over a great number of other metal ions. The association constant for the 1:1 complex was determined to be 2.72 × 10⁷ M^?1.     

Structural requirement of C11b chirality of tetrabenazine analogs as VMAT2 imaging ligands: synthesis and in vivo evaluation

We studied on the structural requirement of C11b chirality of tetrabenazine (TBZ) analogs as vesicular monoamine transporter 2 (VMAT2) ligands. TBZ analogs (2, 6a, 6b) and ¹⁸F-radiolabeled [¹⁸F]6a and [¹⁸F]6b with eliminated C11b chirality were synthesized and characterized. Competition studies demonstrated that 2, 6a and 6b displayed much lower in vivo VMAT2 bindings than TBZ. MicroPET imaging studies of [¹⁸F]6a and [¹⁸F]6b showed negligible accumulation in VMAT2-enriched regions as compared with the known VMAT2 ligand ¹⁸F-FP-(+)-DTBZ. These results suggest that C11b chirality of TBZ analogs is essential for in vivo VMAT2 binding bioactivity.     

POSS-modified PEG adhesives for wound closure

PEG-related adhesives are limited in clinical use because they are easy to swell and cannot support the cell growth.In this study,we produced a series of POSS-modified PEG adhesives with high adhesive strength.Introduction of inorganic hydrophobic POSS units decreased the swelling of the adhesives and enhanced cell adhesion and growth.The in vitro cytotoxicity and in vivo inflammatory response experiments clearly demonstrated that the adhesives were nontoxic and possessed excellent biocompatibility.Compared with the sutured wounds,the adhesive-treated wounds showed an accelerated healing process in wounded skin model of the Bama miniature pig,demonstrating that the POSS-modified PEG adhesive is a promising candidate for wound closure.     

Fluorescent Detection of Cu(Ⅱ) by Chitosan-based AIE Bioconjugate

Detection of Cu(Ⅱ) is very important in disease diagnose, biological system detection and environmental monitoring. Previously, we found that the product TPE-CS prepared by attaching the chromophores of tetraphenylethylene(TPE) to the chitosan(CS) chains showed excellent fluorescent properties. In this study, we tried to use TPE-CS for detecting Cu(Ⅱ) because of the stable complexation of CS with heavy metals and the luminosity mechanism of the Restriction of Intramolecular Rotations(RIR) for aggregation-induced emission(AIE)-active materials. The fluorescence intensity changed when TPE-CS was contacted with different metal ions, to be specific, no change for Na~+, slightly increase for Hg~(2+), Pb~(2+), Zn~(2+), Cd~(2+), Fe~(2+), Fe~(3+) due to the RIR caused by the complexation between CS and metal ions. However, for Cu~(2+), an obvious fluorescence decrease was observed because of the Photoinduced-Electron-Transfer(PET). Moreover, we found that the quenched FL intensity of TPE-CS was proportional to the concentration of Cu(Ⅱ) in the range of 5 μmol/L to 100 μmol/L, which provided a new way to quantitatively detect Cu(Ⅱ) . Besides, TPE-CS has excellent water-solubility as well as absorbability(the percentage of removal, R = 84%), which is an excellent detection probe and remover for Cu(Ⅱ) .     

Thermophilic Dry Methane Fermentation of Distillation Residue Eluted from Ethanol Fermentation of Kitchen Waste and Dynamics of Microbial Communities

Thermophilic dry methane fermentation is advantageous for feedstock with high solid content. Distillation residue with 65.1 % moisture content was eluted from ethanol fermentation of kitchen waste and subjected to thermophilic dry methane fermentation, after adjusting the moisture content to 75 %. The effect of carbon to nitrogen (C/N) ratio on thermophilic dry methane fermentation was investigated. Results showed that thermophilic dry methane fermentation could not be stably performed for >10 weeks at a C/N ratio of 12.6 and a volatile total solid (VTS) loading rate of 1 g/kg sludge/d; however, it was stably performed at a C/N ratio of 19.8 and a VTS loading rate of 3 g/kg sludge/d with 83.4 % energy recovery efficiency. Quantitative PCR analysis revealed that the number of bacteria and archaea decreased by two orders of magnitude at a C/N ratio of 12.6, whereas they were not influenced at a C/N ratio of 19.8. Microbial community analysis revealed that the relative abundance of protein-degrading bacteria increased and that of organic acid-oxidizing bacteria and acetic acid-oxidizing bacteria decreased at a C/N ratio of 12.6. Therefore, there was accumulation of NH₄ ⁺ and acetic acid, which inhibited thermophilic dry methane fermentation.     

Expression and Enzyme Activity Detection of a Sepiapterin Reductase Gene from <Emphasis Type="Italic">Musca domestica</Emphasis> Larva

Tetrahydrobiopterin (BH4) is an essential cofactor for aromatic acid hydroxylases and nitric oxide synthase. Sepiapterin reductase (SPR) catalyzes the final steps of BH4 biosynthesis. Studies on SPR from several insects and other organisms have been reported. However, thus far, enzyme activity of SPR in Musca domestica is kept unknown. In this study, 186 differentially expressed genes including SPR gene from Musca domestica (MDSPR) were screened in subtractive cDNA library. The MDSPR gene was cloned, and the recombinant MDSPI16 protein was expressed as a 51-kDa protein in soluble form. The MDSPR exhibited strong activity to the substrate sepiapterin (SP). The values of V_max and K_m of the MDSPR for SP were 6.83 μM/min and 23.48 μM, and the optimum temperature and pH of MDSPR were 50 °C and 4.0, respectively. This study provides new hypotheses and methods for the production of BH4 using insect-derived SPR.