[Clinical management of skin necrosis after penis lengthening surgery: Report of 12 cases].

OBJECTIVE: To analyze the causes of skin necrosis after penis lengthening surgery and corresponding treatment measures, and observe the clinical effect of free skin graft repair in the treatment of penile skin defects. METHODS: We retrospectively analyzed the clinical data on 12 cases of extensive penile skin necrosis and defect after penis lengthening surgery performed in our department from January 2017 to January 2022. The patients underwent free skin graft repair with medium- or full-thickness skin grafts from the thigh after wound preparation. RESULTS: The skin grafts survived well in all the 12 patients and the incisions healed in the first stage without any complications. At 6 months after surgery, skin sensation was mostly recovered in the area of penis skin grafting, no obvious skin ulceration or edema was observed, and the appearance of the penis was satisfactory. The IIEF-5 scores, Erectile Hardness Scale (EHS) scores, and the results of penile hardness tests of the patients all indicated normal erectile function. CONCLUSION: Free skin graft repair with autologous medium- or full-thickness skin grafts is a safe and effective surgical option for extensive penile skin necrosis after penis lengthening surgery.

[Seminal vesiculoscopy: Safe and effective for the treatment of refractory hemospermia].

OBJECTIVE: To investigate the clinical effect and safety of transutricular seminal vesiculoscopy in the treatment of refractory hemospermia. METHODS: Using 6Fr ureteroscopy through the prostatic utricle, we treated 103 cases of refractory hemospermia with distal seminal duct obstructive lesions, including 12 cases complicated by distal seminal duct cyst. We rinsed the seminal duct cavity, cleaned out the stones, removed the cyst wall with holmium laser and followed up the patients for 12 months postoperatively. RESULTS: The operations were successfully completed in all the cases but 1 (0.9%), in which the ureteroscope failed to enter the bilateral seminal vesicles. The operation time was (47 ± 9) min. No rectal injury or acute epididymitis occurred intraoperatively, nor fever, long-term dysuria or long-term hematuria after surgery. Postoperative follow-up showed that bloody semen symptoms vanished in 93 (90.3%) of the cases, improved significantly in 4 (3.9%) and not significantly in 2 (1.9%), and 3 cases of recurrence (2.9%) were all relieved after reoperation. CONCLUSION: Transutricular seminal vesiculoscopy has the advantages of clear anatomic vision, minor invasiveness and significant effectiveness in the treatment of refractory hemospermia. What's more, holmium laser is better than plasmakinetic resection in removal of the cyst wall.

Mechanistic Insights into the Chemo- and Regio-Selective B(C6F5)3 Catalyzed C-H Functionalization of Phenols with Diazoesters.

The Lewis acidic B(C6F5)3 was recently demonstrated to be effective for the C-H alkylation of phenols with diazoesters. The method avoids the general hydroxyl activation in transition-metal catalysis. Ortho-selective C-H alkylation occurs regardless of potential para-selective C-H alkylation and O-H alkylation. In the present study, a theoretical calculation was carried out to elucidate the reaction mechanism and the origin of chemo- and regio-selectivity. It is found that the previously proposed B(C6F5)3/N or B(C6F5)3/C bonding-involved mechanisms are not favorable, and a more favored one involves the B(C6F5)3/C═O bonding, rate-determining N2 elimination, selectivity-determining electrophilic attack, and proton transfer steps. Meanwhile, the new mechanism is consistent with KIE and competition experiments. The facility of the mechanism is attributed to two factors. First, the B(C6F5)3/C═O bonding reduces the steric hindrance during electrophilic attack. Second, the bonding forms the conjugated system by which the LUMO energy is reduced via the electron-withdrawing B(C6F5)3. The ortho-selectivity resulted from the greater ortho-C-C (than para-C-C) interaction and the O-H···O and O-H···F hydrogen-bond interaction during electrophilic attack. The greater C-C (than C-O) interaction and the π-π stacking between the benzene rings of phenol and diazoester concerted contribute to the chemo-selective C-H alkylation.

Mechanistic Insights into Solvent and Ligand Dependency in Cu(I)-Catalyzed Allylic Alkylation with gem-Diborylalkanes.

The recent Cu-catalyzed allylic substitution reaction between gem-diboryalkane and allyl electrophiles shows intriguing solvent and ligand-controlled regioselectivity. The α-alkylation product was obtained in DMF solvent, while γ-alkylation product was obtained in dioxane solvent and the dioxane and NHC ligand situation. In the present study, density functional theory calculations have been used to investigate the reaction mechanism and origin of the regioselectivity. For both dioxane and DMF, γ-alkylation undergoes successive oxidative addition (CH2Bpin trans to leaving group) and direct Cγ-C reductive elimination. The α-alkylation is found to undergo oxidative addition (CH2Bpin trans to leaving group), isomerization, and Cα-C reductive elimination rather than the previously proposed oxidative addition (-CH2Bpin cis to the leaving group) and Cα-C reductive elimination. The γ-alkylation and α-alkylation is, respectively, favorable for dioxane and DMF solvent, which is consistent with the γ- and α-selectivity in experiment. The solvent interferes the isomerization step, thereby affects the relative facility of the α- and γ-alkylation. Further investigation shows that η1-intermediate formation promoted by solvent is the rate-determining step of the isomerization. The stronger electron-donating ability of DMF than dioxane facilitates the η1-intermediate formation and finally results in the easier isomerization in DMF. For dioxane and NHC situation, in the presence of neutral NHC ligand, the -PO4Et2 group tightly coordinates with the Cu center after the oxidative addition, preventing the isomerization process. The regioselectivity is determined by the relative facility of the oxidative addition step. Therefore, the favorable oxidative addition (in which -CH2Bpin trans to the leaving group) results in the facility of γ-alkylation.

Poly[di-µ(3)-chlorido-di-µ(2)-chlorido-{µ(4)-N,N,N',N'-tetra-kis-[(diphenyl-phosphan-yl)meth-yl]benzene-1,4-diamine-κ(4)P:P':P'':P'''}tetra-copper(II)].

In the title complex, [Cu(4)Cl(4)(C(58)H(52)N(2)P(4))](n), four Cu(II) atoms are held together via two doubly bridging and two triply bridging chlorides, forming a stair-like Cu(4)Cl(4) core having crystallographically imposed inversion symmetry, while the benzene-1,4-diamine ligand (with a crystallographic inversion center at the centroid) acts in a tetra-dentate coordination mode, bridging two adjacent Cu(4)Cl(4) cores, resulting in a chain along the a-axis direction. One Cu atom has a distorted tetra-hedral geometry, coordinated by one P atom, one µ(2)-Cl and two µ(3)-Cl atoms, while the second Cu atom adopts a trigonal geometry, coordinated by one P atom, one µ(2)-Cl and one µ(3)-Cl atoms.

Poly[chlorido[µ(4)-2,2'-(2-methyl-1H-benzimidazol-3-ium-1,3-di-yl)diacetato]-zinc].

The title compound, [Zn(C(12)H(11)N(2)O(4))Cl](n), contains a centrosymmetric dimetal tetra-carboxyl-ate paddle-wheel moiety in which the Zn(II) atom is square-pyramidally coordinated by four carboxyl-ate O atoms at the basal positions and one Cl(-) anion at the apical position. Each paddle-wheel unit is joined to four such neighbours through bridging dicarboxyl-ate ligands, producing a two-dimensional undulating layer parallel to (-101). Adjacent sheets are stacked in a parallel fashion to form a three-dimensional supra-molecular structure which is stabilized by inter-layer π-π inter-actions between benzene rings, with a centroid-centroid distance of 3.722 Å. The range of Zn-O bond lengths is 2.0440 (17)-2.1256 (15) Šand the Zn-Cl bond length is 2.2622 (6) Å.

Electro-activation of O2 on MnO2/graphite felt for efficient oxidation of water contaminants under room condition.

The activation of oxygen (O2) under room condition is highly desirable for oxidative removal of organic pollutants in water. Herein, we report a graphite felt (GF)-supported α-MnO2 catalyst which is active for activating O2 with assistance of an anodic electric field. The electro-assisted catalytic wet air oxidation (ECWAO) process on MnO2/GF is able to rapidly degrade a variety of dyes, pharmaceutics and personal care products (PPCPs) under room condition. The congo red, basic fuchsin, neutral red and methylene blue are completely mineralized in 160 min, and the bisphenol A, triclosan and ciprofloxacin are mineralized by 89.9%, 81.5% and 65.4%, respectively, in 300 min. Mechanistic study indicates a surface-catalyzed non-free radical pathway for the oxidation of organic pollutants by O2 in the ECWAO process. The oxygen vacancies on MnO2 are identified as the catalytically active sites, at which oxygen atom is transferred from O2 to organic molecule through chemisorbed oxygen species. The anodic electric field assists such an oxygen transfer pathway by activating the complex of chemisorbed oxygen species and organic molecule through electro-oxidation reaction. The ECWAO process on MnO2/GF electrode exhibits a great potential for practical wastewater treatment under room condition.

Silicon/Perovskite Core-Shell Heterojunctions with Light-Trapping Effect for Sensitive Self-Driven Near-Infrared Photodetectors.

In this article, we fabricated a sensitive near-infrared (NIR) light detector by directly coating a layer of Cs-doped FAPbI3 perovskite film onto vertical Si nanowire (SiNW) array. The as-assembled SiNW array/perovskite core-shell heterojunction exhibits a typical rectifying characteristic in darkness and distinct photoresponse characteristics under light illumination. Owning to the remarkable photovoltaic effect, the heterojunction can work as a self-driven NIR detector without an exterior energy supply. Further photoresponse investigation reveals that the photodetector is sensitive in a wide wavelength range with maximum sensitivity at ∼850 nm. The responsivity ( R) and specific detectivity ( D*) are estimated to be 14.86 mA W-1 and 2.04 × 1010 Jones at 0 V bias, respectively, which can be improved to 844.33 mA W-1 and 3.2 × 1011 Jones at a bias voltage of -0.9 V. In addition, the present device also possesses distinct advantages of a large Ilight/ Idark ratio exceeding 104, swift response rate with rise/decay times of 4/8 µs, and relatively good ambient stability. According to our numerical simulation based on finite element method, the superior device performance is associated with strong light-trapping effect in such unique core-shell heterojunction array.

[Research on the interaction of aristolochic acid and bovine serum albumin].

The interaction between aristolochic acid and bovine serum albumin (BSA) under physiological conditions was investigated by fluorescence quenching methods. The results indicate that there is a strong interaction between aristolochic acid and BSA, and the distances between the binding location and tryptophan residue is 2.8 nm. The binding location of aristolochic acid in BSA is in subdomain III A. In addition, the effects of aristolochic acid on the protein second structure were studied using CD and FTIR techniques. The results of CD proved that the alpha-helix contents of BSA decreased from 43.5% to 36.7% after binding with aristolochic acid.

[Simultaneous determination of the four effective components in Huaijiao pill by HPLC].

OBJECTIVE: To develop an HPLC method for determination of the four effective components (genistin; rutin; quercetin; genistein) in Huaijiao pill. METHOD: The chromatographic separation was performed on a Shim-packODS (4.6 mm x 150 mm, 5.0 microm) eluted with a mobile phase of MeOH-H2O-HAc (40:60:0.25). The detection wavelength was set at 256 nm and column temperature was set at 30 degrees C . RESULT: Nice linear relation between the peak area and injected amount exists when the amount is within 0.059-0.352 microg for genistin, within 0.435-2.610 microg for rutin, within 0.020-0.121 microg for quercetin and within 0.053-0.319 microg for genistein. The correlation coefficient of each component is 0.999 6, 0.998 2, 0.998 9 and 0.999 9 respectively. The average recoveries of the four components are from 98.7% to 100.2%. The RSD of each group are 1.21%, 1.36%, 0.47% and 1.54% (n = 5). CONCLUSION: The method was accurate, repeatable and suitable to determine four effective components in Huaijiao pill. It can be use for quality control of Huaijiao pill.

A novel role of ethephon in controlling the noxious weed Ipomoea cairica (Linn.) Sweet.

Several auxin herbicides, such as 2, 4-D and dicamba, have been used to eradicate an exotic invasive weed Ipomoea cairica in subtropical China, but restraining the re-explosion of this weed is still a challenge. Since ethylene is one of the major intermediate functioning products during the eradication process, we explored the possibility, mechanism and efficiency of using ethephon which can release ethylene to control Ipomoea cairica. The results of the pot experiment showed that 7.2 g /L ethephon could totally kill Ipomoea cairica including the stems and roots. The water culture experiment indicated that ethephon released an abundance of ethylene directly in leaves and caused increases in electrolyte leakage, 1-aminocyclopropane-1-carboxylic acid (ACC), abscisic acid (ABA) and H2O2 and decreases in chlorophyll content and photosynthetic activity, finally leading to the death of Ipomoea cairica. The field experiment showed that the theoretical effective concentration of ethephon for controlling Ipomoea cairica (weed control efficacy, WCE = 98%) was 4.06 g/L and the half inhibitory concentration (I50) was 0.56 g/L. More than 50% of the accompanying species were insensitive to the phytotoxicity of ethephon. Therefore, ethephon is an excellent alternative herbicide for controlling Ipomoea cairica.

Fluorescence studies of interaction between flavonol p-coumaroylglucoside tiliroside and bovine serum albumin.

In this paper, the interaction between flavonol p-coumaroylglucoside tiliroside and BSA was investigated by fluorescence quenching spectra, synchronous fluorescence spectra, and three-dimensional fluorescence spectra under simulative physiological conditions. It was proved that the fluorescence quenching of BSA by tiliroside was mainly a result of the formation of a tiliroside-BSA complex. The modified Stern-Volmer quenching constant and the corresponding thermodynamic parameters DeltaH, DeltaG and DeltaS at different temperatures were calculated. The results indicated that electrostatic interactions were the predominant intermolecular forces in stabilizing the complex. The distance r=3.95 nm between the donor (BSA) and acceptor (tiliroside) was obtained according to Förster's nonradioactive energy transfer theory. The synchronous fluorescence and three-dimensional fluorescence spectra results showed the microenvironment and conformation of BSA were changed in the binding reaction.