NATURAL PRODUCTS SYNTHESIS BY RETRO-DIELS-ALDER REACTION Ⅱ~1 ASYMMETRIC SYNTHESIS OF (+) AND (-) 5-OXO-ENDO-TRICYCLO [5.2.1.0.^(2, 6)] DECA-3, 8-DIENE 1 BY ENZYME-CATALYZED REACTION

Asymmetric syntheses of both enantiomerically pure (+) and (-) 5-oxo-endo-tricyclo [5.2.1.0.^(2,6)] deca-3, 8-diene 1 was described. The key step is the use of enzyme-catalyzed hydrolysis of meso-diacetate 5.

Sprayable nanodrug-loaded hydrogels with enzyme-catalyzed semiinter penetrating polymer network(Semi-IPN)for solar dermatitis

Solar dermatitis is an acute or chronic high incidence of skin injury caused by ultraviolet(UV)radiation based on strong sunlight,which seriously endangers people's health.In this study,we designed and demonstrated enzyme-catalyzed semi-inter penetrating polymer network(Semi-IPN)sprayable nanodrug-loaded hydrogels based on gelatin,3-(4-hydroxyphenyl)propionic acid(HPA),polyvinyl alcohol(PVA),glycerol,and dexamethasone sodium phosphate(DEXP)for solar dermatitis.The hydrogels had high water content,excellent biocompatibility,effective encapsulation and sustained release of nanodrugs,antiinflammatory,and strong anti-ultraviolet B(anti-UVB)radiation properties based on glycerol and phenol functional groups,but also controllable spray gelation mode to make them adhere well on the dynamic skin surfaces and achieve continuous transdermal drugs delivery for solar dermatitis.The sprayable nanodrug-loaded hydrogel systems could be used as a highly effective therapeutic method for solar dermatitis,and also provide a good strategy for designing novel nanodrug-loaded hydrogel delivery systems.

Enzymatic Synthesis and Characterization of Novel Polycarbonates Derived from 5-Allyloxy-1, 3-dioxan-2-one and 5, 5-Dimethvl-1.3-dioxan-2-one

Novel polycarbonates from 5-allyloxy-1, 3-dioxan-2-one （ATMC） with 5, 5-dimethyl- 1, 3-dioxan-2-one （DTC） were successfully synthesized for the first time using immobilized porcine pancreas lipase （IPPL） as catalyst. The resulting copolymers were characterized by IR, ^1H NMR, ^13C NMR and GPC. The molecular weight （Mn） of the copolymer with molar feed ratio of 10：90 （ATMC：DTC） was 9300 and the polydispersity was 1.31, while the Mn increased to 14300 and polydispersity of 1.25 with the feed ratio of 50：50. Moreover, the composition of the copolymers agreed well with the monomer feed.

Adapting the usage of enzyme unit to its definition

The enzyme unit U, by its definition, is the amount of enzyme that catalyses the transformation o f one micromole of substrate per minute under standard assay conditions. However, in practical use, it is identical with micromole or microgram per minute, which deviates from the essence of the definition as a measure of amount of substance. Such usage appears in many publications that involve enzyme kinetics and conveys obscure signification. In this article, we solved the confusion by regarding the unit U as a measure of amount of enzyme having a specified catalytic activity just like the basic SI unit mole （symbol tool） defined as the amount of substance of a system which contains as many elementary entities as there are atoms in 0.012 kg of carbon 12. We introduced the concept of unit rate, ru, which is defined as the rate of a reaction mediated by 1 U enzyme, in calculating the enzyme units in an amount of enzyme so as to avoid the inconsistence of the expression with the definition of enzyme unit. The method can also be applied to the case of katal, the recommended SI unit of enzyme activity.

Studies on Reduced Extent Method for Inhibited Thermokinetics Of Enzyme－Catalyzed Reaction──Inhibition of the laccase－catalyzed oxidation of o－dihydroxybenzene by m－dihydroxybenzene

The thermokinetic reduced extent equations of reversible inhibitions for Michaiels-Menten enzymatic reaction were deduced, and then the criteria for distingushing inhibition type was given and the methods for calculating kinetic parameters, KM,Ki and Urn were suggested. This theory was applied to inverstigate the inhibited thermokinetics of laccase-catalyzed oxidation of o-dihydroxybenzene by m-dihydroxybenzene. The experimental results show the inhibition belongs to reversible competitive type, KM=6.224×10-3 mol L-1, Ki=2. 363 × 10-2 mol. L-1.

Phosphomonoesterase Activities,Kinetics and Thermodynamics in a Paddy Soil After Receiving Swine Manure for Six Years

Soil phosphomonoesterase plays a critical role in controlling phosphorus(P) cycling for crop nutrition,especially in P-deficient soils.A 6-year field experiment was conducted to evaluate soil phosphomonoesterase activities,kinetics and thermodynamics during rice growth stages after consistent swine manure application,to understand the impacts of swine manure amendment rates on soil chemical and enzymatic properties,and to investigate the correlations between soil enzymatic and chemical variables.The experiment was set out in a randomized complete block design with three replicates and five treatments including three swine manure rates(26,39,and 52 kg P ha^(-1),representing low,middle,and high application rates,respectively) and two controls(no-fertilizer and superphosphate at 26 kg P ha^(-1)).The results indicated that the grain yield and soil chemical properties were significantly improved with the application of P-based swine manure from 0 to 39 kg P ha^(-1);however,the differences between the 39(M_(39)) and 52 kg P ha^(-1) treatments(M_(52)) were not significant.The enzymatic property analysis indicated that acid phosphomonoesterase was the predominant phosphomonoesterase in the tested soil.The M_(39) and M_(52) treatments had relatively high initial velocity(V_0),maximal velocity(V_(max)),and activation grade(lgN_a) but low Michaelis constant(K_m),temperature coefficient(Q_(10)),activation energy(E_a),and activation enthalpy(ΔH),implying that the M_(39) and M_(52) treatments could stimulate the enzyme-catalyzed reactions more easily than all other treatments.The correlation analysis showed that the distribution of soil phosphomonoesterase activities mainly followed the distributions of total C and total N.Based on these results,39 kg P ha^(-1) could be recommended as the most appropriate rate of swine manure amendment.