Microcalorimetric investigation of the effect of berberine alkaloids from <Emphasis Type="Italic">Coptis chinensis</Emphasis> Franch on <Emphasis Type="Italic">Staphylococcus aureus</Emphasis> growth

The inhibitory effects of three berberine alkaloids (BAs) from rhizome of Coptis chinensis Franch, a traditional Chinese medicinal (TCM) herb, on Staphylococcus aureus growth were investigated by microcalorimetry. The power-time curves of S. aureus with and without BAs were acquired; meanwhile the extent and duration of inhibitory effects on the metabolism were evaluated by studying the growth rate constant (k), half inhibitory ratio (IC₅₀), maximum heat-output power (P _max), peak time of maximum heat-output power (t _p) and total heat production (Q _t). The value of k of S. aureus in the presence of the three BAs decreased with the increasing concentrations of BAs. Moreover, P _max was reduced and the value of t _p increased with increasing concentrations of the three drugs. The inhibitory activity varied with different drugs. The values of IC₅₀ of the three BAs are respectively, 101.4 μg/mL for berberine, 241.0 μg/mL for palmatine and 792.3 μg/mL for jateorrhizine. The sequence of antimicrobial activity of the three BAs is: berberine > palmatine > jateorrhizine. It is suggested that the functional group methylenedioxy or methoxyl at C2 on the phenyl ring could possibly improve antimicrobial activity more strongly than hydroxyl at C2 on the phenyl ring. Supported by the National Natural Science Foundation of China (Grant No. 30625042)     

LCST demixing in poly(vinyl methyl ether)/water studied by means of a High Resolution Ultrasonic Resonator

The inhibitory effects of three berberine alkaloids (BAs) from Coptis chinensis Franch on Bifidobacterium adolescentis growth were investigated by microcalorimetry. The growth rate constant (k) and maximum heat-output power (Pmax) decreased and peak time of maximum heat-output power (tp) prolonged with the increase of BAs concentration. Half inhibitory ratios (IC50) BAs were respectively 790.3 (berberine), 339.6 (coptisine) and 229.8 μL⁻¹ (palmatine), which indicated the sequence of their antimicrobial activity: berberine<coptisine<palmatine. Combined with previous findings, the sequence which could show the bioactivity of Bacillus shigae and Escherichia coli was: berberine>coptisine>palmatine. The structure-function relationship of BAs indicated that the functional group methylenedioxy or methoxyl at C2 and C3 might be the major group inducing the activities of BAs on E. coli and B. adolescentis. Meanwhile, the substituent groups at C2, C3, C9 and C10 almost had equal effect on B. shigae.     

Microcalorimetric investigation of the growth of the <Emphasis Type="Italic">Escherichia coli</Emphasis> DH5α in different antibiotics

The effects of Amoxicillin Sodium and Cefuroxime Sodium on the growth of E. coli DH5α were investigated by microcalorimetry. The metabolic power-time curves of E. coli DH5α growth were determined by using a TAM air isothermal microcalorimeter at 37°C. By evaluation of the obtained parameters, such as growth rate constants (k), inhibitory ratio (I), the maximum heat power (P _m) and the time of the maximum heat power (t _m), one found that the inhibitory activity of Amoxicillin Sodium vs. E. coli DH5α is enhanced with the increasing of the Amoxicillin Sodium concentration, and the Cefuroxime Sodium has a stimulatory effect on the E. coli DH5α growth when the concentration is about 1 μg mL⁻¹. The IC₅₀ for the Amoxicillin Sodium and the Cefuroxime Sodium are 1.6 and 2.0 μg mL⁻¹, respectively, it implicates that the E. coli DH5α is more sensitive to Amoxicillin Sodium than Cefuroxime Sodium.     

微量热法比较黄连中四种生物碱的抗菌作用

采用微量热法研究和比较中药黄连中四种生物碱(BAs)的抗菌(大肠杆菌)作用。这四种生物碱分别为小檗碱、黄连碱、巴马汀和药根碱。用LKB-2277生物活性检测系统,以停留法测定了37 ℃时大肠杆菌在BAs作用下的热流功率-时间曲线,并记录生长速率常数k, 指数生长期和稳定期的最大热功率Pm, log、Pm, stat, 生长抑制率I, 传代时间tg,指数生长期的总产热量Qt, log,半数抑菌浓度IC50等热动力学参数。结果显示这四种生物碱具有相异的抗大肠杆菌生长代谢的作用,k, Pm, log和Qt, log值随BAs浓度的增加而相应的减少。综合分析k, Pm, log, Qt, log, I 和IC50值可以看出,BAs抑制大肠杆菌生长代谢强度按小檗碱、黄连碱、巴马汀、药根碱的顺序依次减弱。构效关系研究表明,母环C-2和C-3上连接的亚甲二氧基比甲氧基更能显著增强相应化合物的抗菌作用,而C-9和C-10上连接的亚甲二氧基或甲氧基对这种抗菌作用影响不大。     

Toxic effects of protoberberine alkaloids from <Emphasis Type="Italic">Rhizoma Coptidis</Emphasis> on <Emphasis Type="Italic">Tetrahymena thermophila</Emphasis> BF<Subscript>5</Subscript> growth based on microcalorimetry

Rhizoma Coptidis consists mainly of protoberberine alkaloids (PAs), and has been used for many years as a traditional medicine. Recent research revealed the toxicity of Rhizoma Coptidis, but studies focusing on the relationships between the structures of PAs and their toxicities are lacking. The toxic effects of four PAs from Rhizoma Coptidis on the growth of Tetrahymena thermophila BF₅ were investigated by microcalorimetry. The power-time curves of T. thermophila BF₅ with and without PAs were obtained; the extent and duration of toxic effects on the metabolism of this organism were evaluated by studying thermokinetic parameters and the half-inhibitory ratio (IC ₅₀). All the thermokinetic parameters showed regular variations with alteration of PA concentrations. The magnitude of the toxic effects of PAs was ascertained from IC ₅₀ values: palmatine > jateorhizine > berberine ≈ coptisine. The structure–function relationship of PAs indicated that the C2 and C3 positions contributed more to the toxic effect of PAs. That is, when substituted with methoxyl groups, the toxic effect would be increased.     

Cytotoxic phenolic glycosides from <Emphasis Type="Italic">Boschniakia himalaica</Emphasis>

A new lignan glycoside, 9-acetyl lanicepside B (1), was isolated from the whole plant of Boschniakia himalaica, along with five known compounds, lanicepside A (2), plantainoside D (3), plantamajoside (4), (–)-woonenoside XI (5), and syringin (6). The new compound's structure was established on the basis of detailed 1D and 2D NMR spectroscopic analysis and chemical evidence. 9-Acetyl lanicepside B (1) showed weak in vitro cytotoxic activities against A549 and P388 with IC₅₀ values of 64.7 μM and 72.5 μM, respectively. Syringin (6) showed moderate in vitro cytotoxic activities against A549 and HL-60 with IC₅₀ values of 32.5 μM and 41.8 μM, respectively.     

Phytochemical Study on Some Polyphenols of <Emphasis Type="Italic">Geranium pyrenaicum</Emphasis>

In order to continue our previous studies concerning Geranium pyrenaicum Burm. (Geraniaceae), we have performed spectrophotometric determinations and a HPLC study of some polyphenols. We have analyzed the dried Geranii pyrenaici herba (harvested from Cluj-Napoca, district of Cluj, Romania). We have established the content in flavonoids (0.316%), phenolic acids (0.099%), tannins (5.295%), and anthocyanins (12.030 mg/100 g vegetal product). We have identified and measured by HPLC the following compounds: hyperoside (21.61 μg/100 mg), ellagic acid (1810.44 μg/100 mg), isoquercitrine (11.197 μg/100 mg), and caftaric acid (76.83 μg/100 mg). We have also analyzed by HPLC a hydrolyzed sample of the same drug in which we have identified and measured: ellagic acid (4139.33 μg/100 mg), quercetol (29.65 μg/100 mg), kaempherol (41.48 μg/100 mg), and caftaric acid (20.721 μg/100 mg). __________ Published in Khimiya Prirodnykh Soedinenii, No. 4, pp. 322–324, July–August, 2005.     

Kinetic Isotope Effect in the Photoreduction of <Emphasis Type="Italic">o</Emphasis>-Benzoquinones in the Presence of <Emphasis Type="Italic">N,N</Emphasis>-Dimethylaniline

The kinetics of photoinduced reduction of a series of 3,5- and 3,6-di-tert-butylbenzoquinones-1,2 was studied in the presence of N,N-dimethylaniline, its deuterated analog, and a series of para-substituted N, N-dimethylanilines. On passing from the endothermic to the exothermic range of the free energy of electron transfer ΔG _e , the effective rate constants k _H and k _D and the quantum yields ϕ_H and ϕ_D of the reaction varied nonmonotonically with a maximum at ΔG _e of approximately +0.1 eV. For the reactant pairs relevant to the ascending (left-hand) branch of the plot k _H = f(ΔG _e ), the H/D isotope effect takes place, varying from two to five in magnitude. For the reactant pairs at the maximum and in the descending (right-hand) branch of the plot k _H = f(ΔG _e ), there is no isotope effect or its value is insignificant.__________Translated from Khimiya Vysokikh Energii, Vol. 39, No. 5, 2005, pp. 348–352.Original Russian Text Copyright © 2005 by Abakumov, Shurygina, Chesnokov, Druzhkov, Lopatin, Chechet, Cherkasov.     

Porric acid D from marine-derived fungus <Emphasis Type="Italic">Alternaria</Emphasis> sp. isolated from Bohai Sea

Porric acid D (1), a new dibenzofuran derivative, was isolated from the methanol extract of a marine-derived fungus, Alternaria sp., isolated from the Bohai Sea, together with a known compound, altenusin. Their structures were elucidated by spectroscopic analysis, including high-resolution mass spectroscopy, and 1 and 2-dimensional NMR techniques. Compounds 1 and 2 showed inhibitory activity against Staphyloccocus aureus with MIC 100 and 25 μg/mL, respectively.     

Heat capacity of <Emphasis Type="Italic">D</Emphasis>- and <Emphasis Type="Italic">DL</Emphasis>-serine in a temperature range of 5.5 to 300 K

Heat capacity of D- and DL-serine was measured using adiabatic calorimetry in a temperature range of 5.5 to 300 K, and then thermodynamic functions were calculated. The difference in heat capacity (C _PD-C _PDL) between two species indicates a small anomaly in D-serine near 15 K and a systematic excess over DL for temperatures > 30 K. This is much larger, than a difference in thermodynamic functions measured so far for the polymorphs of organic molecular crystals. The excess is fitted well to Einstein contribution with characteristic temperature of 185 K which is equivalent to vibrational mode at 129 cm⁻¹.     

Study on Inclusion Complex Formation of <Emphasis Type="Italic">m</Emphasis>-Aminobenzoic Acid with Native and Substituted <Emphasis Type="Italic">β</Emphasis>-Cyclodextrins

The complex formation of native and substituted β-cyclodextrins with m-aminobenzoic acid in water was characterized by calorimetry, ¹H NMR and UV spectroscopic studies. These studies showed that β-, hydroxypropyl-β- and methyl-β-cyclodextrins form 1:1 inclusion complexes with m-aminobenzoic acid. The thermodynamic properties of complex formation (K,Δ_c G ^o,Δ_c H ^o,Δ_c S ^o) were calculated. It was found that the processes of complexation are mainly favorable entropically. Introduction of hydroxypropyl- and methyl-substituents into the β-CD molecule results in negligible enhancement of stability of the complexes formed. The structure of these substituents has no influence on the stability constant values. The insertion of the carboxylic group of m-aminobenzoic acid into the cyclodextrin cavity was confirmed by ¹H NMR data.     

Application of the <Emphasis Type="Italic">k</Emphasis><Subscript>0</Subscript>-NAA method at the HANARO research reactor

The k ₀-standardization method (k ₀-NAA) is known as one of the most remarkable progresses of the NAA with its many advantages. For the application of k ₀-NAA method at the NAA #1 irradiation position where the neutrons are well thermalized in the HANARO research reactor, KAERI, Korea, the determination of the reactor neutron spectrum parameters such as α and f have been carried out. The measured values of α and f using the “Cd-ratio” triple monitor method were 0.127±0.022 and 1010±70, respectively. To evaluate the applicability of k ₀-NAA in our analytical system, the analysis of three kinds of SRMs was executed. The analytical results showed that the relative error of most of the elements was less than 10% and the U-scores were within 2. It is turned out that the procedure of the k ₀-NAA in the HANARO research reactor is available for a practical application in the environmental fields.     

Mechanistic study of the oxidation of N-phenyldiethanolamine by <Emphasis Type="Italic">bis</Emphasis>(hydrogen periodato)argentate(III) complex anion

The kinetics of oxidation of phenyldiethanolamine (PEA) by a silver(III) complex anion, [Ag(HIO₆)₂]⁵⁻, has been studied in an aqueous alkaline medium by conventional spectrophotometry. The main oxidation product of PEA has been identified as formaldehyde. In the temperature range 20.0–40.0 °C , through analyzing influences of [OH⁻] and [IO ₄ ⁻ ]_tot on the reaction, it is pseudo-first-order in Ag(III) disappearance with a rate expression: k _obsd = (k ₁ + k ₂[OH⁻]) K ₁ K ₂[PEA]/{f([OH⁻])[IO ₄ ⁻ ]_tot + K ₁ + K ₁ K ₂ [PEA]}, where k ₁ = (0.61 ± 0.02) × 10⁻² s⁻¹, k₂ = (0.049 ± 0.002) M⁻¹ s⁻¹ at 25.0 °C and ionic strength of 0.30 M. Activation parameters associated with k ₁ and k ₂ have also been derived. A reaction mechanism is proposed involving two pre-equilibria, leading to formation of an Ag(III)-periodato-PEA ternary complex. The ternary complex undergoes a two-electron transfer from the coordination PEA to the metal center via two parallel pathways: one pathway is spontaneous and the other is assisted by a hydroxide ion.     

Average inner and outer radii in singly-excited 1<Emphasis Type="Italic">snl</Emphasis> states of the He atom

Average inner < r _< > and outer < r _> > radii are studied for 28 singly-excited 1 snl singlet and triplet states (0 ≤ l ≤ n ≤ 5) of the He atom. In all the cases, the average inner radius < r _< > is close to 0.75 bohr, which indicates that one of the two electrons behaves like the 1s electron in He⁺. On the other hand, an analysis of the average outer radius < r _> > shows that the other electron of the 1snl states behaves approximately like an snl electron in the hydrogen atom. The average outer radius < r _> > reflects more diffuse character of the singlet electron distribution. This paper is dedicated to the late Professor Serafin Fraga for his great contribution to quantum sciences. Contribution to the Serafin Fraga Memorial Issue.     

Host–Guest Complexation of <Emphasis Type="Italic">β</Emphasis>-, <Emphasis Type="Italic">γ</Emphasis>-Cyclodextrin with Alkyl Trimethyl Ammonium Bromides in Aqueous Solution

As a continuation of our previous investigation, interactions between cyclodextrin (β-CD), γ-cyclodextrin (γ-CD) and alkyl trimethylammonium bromides in aqueous solutions have been studied with titration calorimetry and ¹H NMR at 298.15 K. The results are discussed in terms of the amphiphilic interaction of CD with surfactants and the iceberg structure formed by water molecules existing around the hydrophobic tail of surfactant molecules. The stoichiometry of the β-CD–surfactant system is 1:1 whereas that of the γ-CD–surfactant system is 1:2. The corresponding formation enthalpy (negative) of the complexes of the two systems decreases with an increase in the number of carbon atoms (n) in hydrophobic chain of surfactant molecule, C _n H_2n+1, whereas the entropy increases with the enlargement of n.     

Synthesis from geraniol of (2<Emphasis Type="Italic">E</Emphasis>,6<Emphasis Type="Italic">E</Emphasis>,10<Emphasis Type="Italic">E</Emphasis>,14<Emphasis Type="Italic">E</Emphasis>)-16-hydroxygeranylgeraniol and some of its derivatives

Several α,ω-bifunctional derivatives of E,E,E-geranylgeraniol were prepared via convergent synthesis starting with geraniol (8), which was converted in three steps into the tetrahydropyranyl ether of 8-chlorogeraniol (9) and 8-hydroxygeranylphenylsulfone (10). Combination of synthons 9 and 10 with subsequent reductive removal of the phenylsulfonyl group produced the tetrahydropyranyl ether of ω-hydroxygeranylgeraniol (5), hydrolysis of which gave exclusively trans-ω-hydroxygeranylgeraniol (1). Derivatives 5–7 of geranylgeraniol were synthesized using standard methods. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 231–234, May–June, 2007.     

Separation and identification of steroidal compounds with cytotoxic activity against human gastric cancer cell lines <Emphasis Type="Italic">in vitro</Emphasis> from the rhizomes of <Emphasis Type="Italic">Paris polyphylla</Emphasis> var. <Emphasis Type="Italic">chinensis</Emphasis>

A novel steroidal saponin, along with 12 known steroidal compounds, was isolated from the rhizomes of Paris polyphylla var. chinensis. Spectral data, including two-dimensional NMR, showed that the structure of the novel saponin was 3β,21-dihydroxypregnane-5-en-20S-(22,16)-lactone-1-O-α-L-rhamnopyranosyl(1→2)-[β-D-xylopyranosyl(1→3)]-β-D-glucopyranoside. The isolated steroidal compounds were evaluated for their cytotoxic activity on human gastric cancer cell line HepG₂, SGC7901, BxPC3. Diosgenin-3-O-α-L-rhamnopyranosyl(1→2)[α-L-rabinofuranosyl(1→4)]-β-D-glucopyranoside exhibited the most potent cytotoxic activity among the isolated steroids. Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 556–560, November–December, 2007.     

Reaction sites of <Emphasis Type="Italic">N,N′</Emphasis>-substituted <Emphasis Type="Italic">p</Emphasis>-phenylenediamine antioxidants

The geometries of N,N′-diphenylbenzene-1,4-diamine (DPPD), N-phenyl-N′-(1-phenylethyl)benzene-1,4-diamine (SPPD), N-(4-methylpentan-2-yl)-N′-phenylbenzene-1,4-diamine (6PPD), N-propan-2-yl-N′-phenylbenzene-1,4-diamine (IPPD), N-(2-methoxybenzyl)-N′-phenylbenzene-1,4-diamine (MBPPD), and N-phenyl-N′-(2-phenylpropan-2-yl)benzene-1,4-diamine (CPPD) as well as of their dehydrogenation products were optimized by the semiempirical AM1 method. The results support the idea of stable N_B=C_X structures formation during the consecutive dehydrogenation of SPPD, 6PPD, IPPD, and MBPPD antioxidants. The biradicals formed during the second step of dehydrogenation of substituted phenylenediamines might be important for their antioxidant effectiveness. Dedicated to Professor Vladimír Kvasnička, DrSc., in honour of his 65th birthday     

Mercaptan addition to 1-<Emphasis Type="Italic">O</Emphasis>-allyl-2,3,4,6-tetra-<Emphasis Type="Italic">O</Emphasis>-acetyl-<Emphasis Type="Italic">β</Emphasis>-D-galactopyranose

Addition of ethyl-, propyl-, and n-butylmercaptans to 1-O-allyl-2,3,4,6-tetra-O-acetyl-β-D-galactopyranose in the presence of benzoyl peroxide catalyst was studied for the first time. The products were 1-O-(3-ethylthiopropyl)-2,3,4,6-tetra-O-acetyl-β-D-galactopyranose, 1-O-(3-propylthiopropyl)-2,3,4,6-tetra-O-acetyl-β-D-galactopyranose, and 1-O-(3-butylthiopropyl)-2,3,4,6-tetra-O-acetyl-β-D-galactopyranose. Deacetylation of 1-O-(3-ethylthiopropyl)-2,3,4,6-tetra-O-acetyl-β-D-galactopyranose produced 1-O-(3-ethylthiopropyl)-β-D-galactopyranose. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 209–211, May–June, 2007.     

Biotransformation of methyltestosterone by the filamentous fungus <Emphasis Type="Italic">Mucor racemosus</Emphasis>

Fungi have proved to be powerful biocatalysts in steroid biotransformations. In the present study, the soil isolate filamentous fungus Mucor racemosus was applied for bioconversion of methyltestosterone (1), an anabolic steroid, in a five-day fermentation. Microbial metabolites were purified chromatographically and identified on the basis of their spectral data as 7α-hydroxymethyltestosterone (2), 15α-hydroxymethyltestosterone (3), and 12,15α-dihydroxymethyltestosterone (4). Observed modifications were hydroxylations at C-7α, C-12, and 15α-positions. Best fermentation condition for production of hydroxylated derivatives was found to be 25°C at 150 rpm for 5 days with a substrate concentration of 1 mg/mL.