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Dr. Fa-Jie Chen Dr. Jianmin Gao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(66):e202201843
Cysteine bioconjugation serves as a powerful tool in biological research and has been widely used for chemical modification of proteins, constructing antibody-drug conjugates, and enabling cell imaging studies. Cysteine conjugation reactions with fast kinetics and exquisite selectivity have been under heavy pursuit as they would allow clean protein modification with just stoichiometric amounts of reagents, which minimizes side reactions, simplifies purification and broadens functional group tolerance. In this concept, we summarize the recent advances in fast cysteine bioconjugation, and discuss the mechanism and chemical principles that underlie the high efficiencies of the newly developed cysteine reactive reagents. 相似文献
3.
Claudius Gros 《Entropy (Basel, Switzerland)》2021,23(2)
Human societies are characterized by three constituent features, besides others. (A) Options, as for jobs and societal positions, differ with respect to their associated monetary and non-monetary payoffs. (B) Competition leads to reduced payoffs when individuals compete for the same option as others. (C) People care about how they are doing relatively to others. The latter trait—the propensity to compare one’s own success with that of others—expresses itself as envy. It is shown that the combination of (A)–(C) leads to spontaneous class stratification. Societies of agents split endogenously into two social classes, an upper and a lower class, when envy becomes relevant. A comprehensive analysis of the Nash equilibria characterizing a basic reference game is presented. Class separation is due to the condensation of the strategies of lower-class agents, which play an identical mixed strategy. Upper-class agents do not condense, following individualist pure strategies. The model and results are size-consistent, holding for arbitrary large numbers of agents and options. Analytic results are confirmed by extensive numerical simulations. An analogy to interacting confined classical particles is discussed. 相似文献
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Let x=(x',x')with x'∈Rk and x'∈R^N-k andΩbe a x'-symmetric and bounded domain in R^N(N≥2).We show that if 0≤a≤k-2,then there exists a positive constant C>0 such that for all x'-symmetric function u∈C0^∞(Ω)with∫Ω|■u(x)|^N-a|x'|^-adx≤1,the following uniform inequality holds1/∫Ω|x|^-adx∫Ωe^βa|u|N-a/N-a-1|x'|^-adx≤C,whereβa=(N-a)(2πN/2Γ(k-a/2)Γ(k/2)/Γ(k/2)r(N-a/2))1/N-a-1.Furthermore,βa can not be replaced by any greater number.As the application,we obtain some weighted Trudinger–Moser inequalities for x-symmetric function on Grushin space. 相似文献
6.
We consider the random‐cluster model (RCM) on with parameters p∈(0,1) and q ≥ 1. This is a generalization of the standard bond percolation (with edges open independently with probability p) which is biased by a factor q raised to the number of connected components. We study the well‐known Fortuin‐Kasteleyn (FK)‐dynamics on this model where the update at an edge depends on the global geometry of the system unlike the Glauber heat‐bath dynamics for spin systems, and prove that for all small enough p (depending on the dimension) and any q>1, the FK‐dynamics exhibits the cutoff phenomenon at with a window size , where λ∞ is the large n limit of the spectral gap of the process. Our proof extends the information percolation framework of Lubetzky and Sly to the RCM and also relies on the arguments of Blanca and Sinclair who proved a sharp mixing time bound for the planar version. A key aspect of our proof is the analysis of the effect of a sequence of dependent (across time) Bernoulli percolations extracted from the graphical construction of the dynamics, on how information propagates. 相似文献
7.
In this study, we perform a series of mass-balance-type calculations, in order to estimate the minimum volume of liquid water required to dissolve completely a single methane gas bubble, located inside different types of domains that are near or under hydrate equilibrium pressure/temperature conditions. We examine the case of methane bubble dissolution in the bulk, along with the cases of methane bubble dissolution within simple/regular networks of pores, where all pores have the same size. In our calculations, we consider experimental values for the equilibrium solubilities of methane in water, along the hydrate-forming line, as well as, values obtained from predictive tools that are based on different thermodynamic models. The effect of aqueous NaCl solutions on the results is also investigated. As a result of the relatively low solubility of methane in water, large volumes of water are required for complete dissolution of a methane bubble. 相似文献
8.
Benni Du 《Molecular physics》2020,118(2)
Kinetics and mechanism of the gas-phase reaction of CH3C(O)OCH(CH3)CH2OCH3 (MPA) with OH radicals in the presence of O2 and NO have been investigated theoretically by performing a high and reliable level of theory, viz., CCSD(T)/6-311?+?G(d,p)//BH&HLYP/6-311++G(d,p)?+?0.9335×ZPE. The calculations predict that the H-abstraction from the ?CH2?O? position of MPA is the most facile channel, which leads to the formation of the corresponding alkoxy radicals CH3C(O)OCH(CH3)C(O ?)HOCH3 under atmospheric conditions. This activated radicals CH3C(O)OCH(CH3)C(O ?)HOCH3 will undergo further rearrangement, fragmentation and oxidative reactions and predominantly leads to the formation of various products (methyl formate HC(O)OCH3 and acetic anhydride CH3C(O)OC(O)CH3). In the presence of water, acetic anhydride can convert into acetic acid CH3C(O)OH via the hydrolysis reaction. The calculated total rate constants over the temperature range 263–372?K are used to derive a negative activation energy (Ea= ?5.88 kJ/mol) and an pre-exponential factor (A?=?1.78×10?12 cm3 molecule?1 s?1). The obtained Arrhenius parameters presented here are in strong agreement with the experimental values. Moreover, the temperature dependence of the total rate constant over a temperature range of 263?1000?K can be described by k?=?5.60 × 10?14×(T/298?K)3.4×exp(1725.7?K/T) cm3 molecule?1 s?1. 相似文献
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10.
Lucie Bielská Jakub Hofman 《International journal of environmental analytical chemistry》2015,95(7):635-649
The proper choice of exposure times is critical if the freely dissolved concentration of chemicals in soil porewater is to be measured via the equilibrium solid-phase microextraction (SPME) as the times to equilibrium may vary depending on compound and soil properties. To reveal the effects of compound hydrophobicity, ageing and soil organic matter content on times to equilibrium, the SPME uptake was measured for five freshly added and aged hydrophobic organic compounds (phenanthrene, pyrene, lindane, p,p′-DDT and polychlorinated biphenyl (PCB) 153) in two contrasted soils (arable and forest soil). The tested compound-soil systems behaved kinetically different. Longer equilibrium times were observed with increasing hydrophobicity of compounds for aged compared to freshly added chemicals and for the forest soil in comparison to the arable soil. The calculated soil–porewater partition coefficients (i.e. sorption coefficients, Kd) of chemicals differed between soil types mainly due to various organic carbon (OC) contents as evidenced by the comparable Koc values (i.e. Kd values normalised to soil OC content). Similar Koc values were also found with the various extent of ageing, indicating that both the freshly added and aged compounds linearly partitioned between the soil organic matter and porewater. Our results suggest that, for a respective compound, variations in equilibrium times may be expected depending upon the residence time and the organic matter content in soil where the longest equilibrium times seems to appear for a combination of aged compounds and high organic soils. With regard to this outcome, the effect of the level of sample depletion due to the SPME extraction (LDSPME) on equilibrium times was assessed. At LDsSPME of up to 10%, equilibrium times increases linearly with LDsSPME for p,p′-DDT and PCB 153. For phenanthrene (LDSPME<10%), and for lindane and pyrene (1.2% < LDSPME > 40%), no clear relationships were observed. 相似文献