Hitherto-Unexplored Photodynamic Therapy of Ag2S and Enhanced Regulation Based on Polydopamine In Vitro and Vivo

Given their superior penetration depths, photosensitizers with longer absorption wavelengths present broader application prospects in photodynamic therapy (PDT). Herein, Ag₂S quantum dots were discovered, for the first time, to be capable of killing tumor cells through the photodynamic route by near-infrared light irradiation, which means relatively less excitation of the probe compared with traditional photosensitizers absorbing short wavelengths. On modification with polydopamine (PDA), PDA-Ag₂S was obtained, which showed outstanding capacity for inducing reactive oxygen species (increased by 1.69 times). With the addition of PDA, Ag₂S had more opportunities to react with surrounding O₂, which was demonstrated by typical triplet electron spin resonance (ESR) analysis. Furthermore, the PDT effects of Ag₂S and PDA-Ag₂S achieved at longer wavelengths were almost identical to the effects produced at 660 nm, which was proved by studies in vitro. PDA-Ag₂S showed distinctly better therapeutic effects than Ag₂S in experiments in vivo, which further validated the enhanced regulatory effect of PDA. Altogether, a new photosensitizer with longer absorption wavelength was developed by using the hitherto-unexplored photodynamic function of Ag₂S quantum dots, which extended and enhanced the regulatory effect originating from PDA.     

Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis

Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β^2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis.     

Characteristics of black carbon aerosol in Jiaxing,China during autumn 2013

We conducted measurements of black carbon（BC） aerosol in Jiaxing,China during autumn from September 26 to November 30,2013.We investigated temporal and diurnal variations of BC,and its correlations with meteorological parameters and other major pollutants.Results showed that hourly mass concentrations of BC ranged from 0.2 to 22.0 μg/m³,with an average of 5.1 μg/m³.The diurnai variation of BC exhibited a bimodal distribution,with peaks at 07:00 and 18:00.The morning peak was larger than the evening peak.The mass percentages of BC in PM_2.5 and PM₁₀ were 7.1%and 4.8%,respectively.The absorption coefficient of BC was calculated to be 44.4 Mm^-1,which accounted for 11.1%of the total aerosol extinction.BC was mainly emitted from local sources in southwestern Jiaxing where BC concentrations were generally greater than 11 μg/m³ during the measurement period.Correlation analysis indicated that the main sources of BC were motor vehicle exhaust,and domestic and industrial combustion.     

Mass and isotopic concentrations of water-insoluble refractory carbon in total suspended particulates at Mt.Waliguan Observatory(China)

Mass concentration and isotopic values δ¹³C and ¹⁴C are presented for the water-insoluble refractory carbon（WIRC） component of total suspended particulates（TSP）,collected weekly during 2003,as well as from October 2005 to May 2006 at the WMO-GAW Mt.Waliguan（WLG） site.The overall average WIRC mass concentration was（1183±120）ng/m³（n = 79）,while seasonal averages were 2081 ±1707（spring）,454±205（summer）,650±411（autumn）,and 1019±703（winter） ng/m3.Seasonal variations in WIRC mass concentrations were consistent with black carbon measurements from an aethalometer,although WIRC concentrations were typically higher,especially in winter and spring.The δ¹³C PDB value（-25.3 ± 0.8）%.determined for WIRC suggests that its sources are C₃ biomass or fossil fuel combustion.No seasonal change in δ¹³C PDB was evident.The average percent Modern Carbon（pMC） for ¹⁴C in WIRC for winter and spring was（67.2 ± 7.7）%（n = 29）.Lower pMC values were associated with air masses transported from the area east of WLG,while higher pMC values were associated with air masses from the Tibetan Plateau,southwest of WLG.Elevated pMC values with abnormally high mass concentrations of TSP and WIRC were measured during a dust storm event.     

Gauge natural formulation of conformal gravity

We consider conformal gravity as a gauge natural theory. We study its conservation laws and superpotentials. We also consider the Mannheim and Kazanas spherically symmetric vacuum solution and discuss conserved quantities associated to conformal and diffeomorphism symmetries.