Cyclo[18]carbon has received considerable attention thanks to its novel geometric configuration and special electronic structure.Superalkalis have low ionization energy.Doping a superalkali in cyclo[18]carbon is an ef...Cyclo[18]carbon has received considerable attention thanks to its novel geometric configuration and special electronic structure.Superalkalis have low ionization energy.Doping a superalkali in cyclo[18]carbon is an effective method to improve the optical properties of the system because considerable electron transfer occurs.In this paper,the geometry,bonding properties,electronic structure,absorption spectrum,and nonlinear optical(NLO)properties of superalkaline M_(3)O(M=Li,Na)-doped cyclo[18]carbon were studied by using density functional theory.M_(3)O and the C_(18) rings are not coplanar.The C_(18) ring still exhibits alternating long and short bonds.The charge transfer between M_(3)O and C_(18) forms stable[M_(3)O]+[C_(18)]-ionic complexes.C_(18)M_(3)O(M=Li,Na)shows striking optical nonlinearity,i.e.,their first-and second-order hyperpolarizability(βvec andγ||)increase considerably atλ=1907 nm and 1460 nm.展开更多
This is a prospective interventional clinical study evaluating intraocular inflammation developed after Ultrasound Cyclo Plasty(UCP) for the treatment of glaucoma. Eighteen eyes of 18 patients were treated with UCP se...This is a prospective interventional clinical study evaluating intraocular inflammation developed after Ultrasound Cyclo Plasty(UCP) for the treatment of glaucoma. Eighteen eyes of 18 patients were treated with UCP second-generation probes(Eye OP1). After treatment, the mean intraocular pressure(IOP) significantly decreased from 26.8±7.2 to 18.8±6.1 mm Hg at day 1 and to 14.7±3.4 mm Hg at month 6(all P<0.001). Mean laser flare-cell photometry value steeply increased after surgery from 12.1±7.5 to 64.1±53.9 ph/ms(P=0.001) at day 1, and then progressively decreased to respectively 60.6±49.7 at day 7, 43.5±38.5 at day 14 and 28.2±18.3 at month 1(all P<0.05), returning at levels similar to baseline ones at month 3 and month 6(respectively 16.7±6.2 and 12.8±10.2, both P>0.05). A significant negative correlation was found between postoperative increase of aqueous flare values and anterior chamber depth(R=-0.568, P=0.014). This timeframe may be considered reasonable for repeating UCP treatment, when required.展开更多
A new cyclodipeptide, cyclo(phenylalanyl-N-methyltyrosyl) 1, was isolated from the mycelial solid cultures of Geotrichum candidum. Its structure was elucidated by spectroscopic methods. The antifungal activity of the ...A new cyclodipeptide, cyclo(phenylalanyl-N-methyltyrosyl) 1, was isolated from the mycelial solid cultures of Geotrichum candidum. Its structure was elucidated by spectroscopic methods. The antifungal activity of the new compound against Peronophythora litchii was assessed by microplate Alamar blue assay (MABA).展开更多
Cyclocarbon fully consists of sp-hybridized carbon atoms,which shows quite unusual electronic and geometric structures compared to common molecules.In this work,we systematically studied strain energy(SE)of cyclocarbo...Cyclocarbon fully consists of sp-hybridized carbon atoms,which shows quite unusual electronic and geometric structures compared to common molecules.In this work,we systematically studied strain energy(SE)of cyclocarbons of different sizes using regression analysis method based on electronic energies evaluated at the very accurate DLPNO-CCSD(T)/ccp VTZ theoretical level.In addition,ring strain of two systems closely related to cyclocarbon,boron nitride(BN)ring,and cyclic polyacetylene(c-PA),is also explored.Very ideal relationships between SE and number of repeat units(n)are built for cyclo[2n]carbon,B_(n)N_(n),and[2n]c-PA as SE=555.0·n^(-1),145.1·n^(-1),and 629.8·n^(-1)kcal·mol^(-1),respectively,and the underlying reasons of the difference and similarity in their SEs are discussed from electronic structure perspective.In addition,force constant of harmonic potential of C-C-C angles in cyclocarbon is derived based on SE values,the result is found to be 56.23 kcal·mol^(-1)·rad^(-2).The possibility of constructing homodesmotic reactions to calculate SEs of cyclocarbons is also explored in this work,although this method is far less rigorous than the regression analysis method,its result is qualitatively correct and has the advantage of much lower computational cost.In addition,comparisons show thatωB97XD/def2-TZVP is a good inexpensive alternative to the DLPNO-CCSD(T)/cc-p VTZ for evaluating energies used in deriving SE,while the popular and very cheap B3LYP/6-31G(d)level should be used with caution for systems with global electron conjugation such as c-PA.展开更多
Treatment of 1,3-di- t -butylcyclopentadiene with rhodium trichloride in EtOH leads to the formation of binuclear half-sandwich complex [Cp t RhCl( μ -Cl)] 2 (1) (Cp t = η 5- t Bu 2C 5H 3) which reacts with trimethy...Treatment of 1,3-di- t -butylcyclopentadiene with rhodium trichloride in EtOH leads to the formation of binuclear half-sandwich complex [Cp t RhCl( μ -Cl)] 2 (1) (Cp t = η 5- t Bu 2C 5H 3) which reacts with trimethylphosphine to give Cp t Rh(PMe 3)Cl 2(2) in high yield. 2 reacts with ammonium polysulfide, (NH 4) 2S x to give cyclooligosulfido half-sandwich complexes Cp t Rh(PMe 3)(S n )( n =4(4a),6(4b)). Desulfurization of 4b by excess PPh 3 results in cyclotetrasulfido product 4a, while 4a takes up sulfur from polysulfide to convert cyclohexasulfido product 4b. The reaction of 2 with Et 4NI gives diiodide complex 3 which is determined by single crystal X-ray crystallographic analysis.展开更多
基金Project supported by the Natural Science Foundation of Anhui Province(Grant No.1908085MA12)the National Natural Science Foundation of China(Grant No.21703222)。
文摘Cyclo[18]carbon has received considerable attention thanks to its novel geometric configuration and special electronic structure.Superalkalis have low ionization energy.Doping a superalkali in cyclo[18]carbon is an effective method to improve the optical properties of the system because considerable electron transfer occurs.In this paper,the geometry,bonding properties,electronic structure,absorption spectrum,and nonlinear optical(NLO)properties of superalkaline M_(3)O(M=Li,Na)-doped cyclo[18]carbon were studied by using density functional theory.M_(3)O and the C_(18) rings are not coplanar.The C_(18) ring still exhibits alternating long and short bonds.The charge transfer between M_(3)O and C_(18) forms stable[M_(3)O]+[C_(18)]-ionic complexes.C_(18)M_(3)O(M=Li,Na)shows striking optical nonlinearity,i.e.,their first-and second-order hyperpolarizability(βvec andγ||)increase considerably atλ=1907 nm and 1460 nm.
文摘This is a prospective interventional clinical study evaluating intraocular inflammation developed after Ultrasound Cyclo Plasty(UCP) for the treatment of glaucoma. Eighteen eyes of 18 patients were treated with UCP second-generation probes(Eye OP1). After treatment, the mean intraocular pressure(IOP) significantly decreased from 26.8±7.2 to 18.8±6.1 mm Hg at day 1 and to 14.7±3.4 mm Hg at month 6(all P<0.001). Mean laser flare-cell photometry value steeply increased after surgery from 12.1±7.5 to 64.1±53.9 ph/ms(P=0.001) at day 1, and then progressively decreased to respectively 60.6±49.7 at day 7, 43.5±38.5 at day 14 and 28.2±18.3 at month 1(all P<0.05), returning at levels similar to baseline ones at month 3 and month 6(respectively 16.7±6.2 and 12.8±10.2, both P>0.05). A significant negative correlation was found between postoperative increase of aqueous flare values and anterior chamber depth(R=-0.568, P=0.014). This timeframe may be considered reasonable for repeating UCP treatment, when required.
文摘A new cyclodipeptide, cyclo(phenylalanyl-N-methyltyrosyl) 1, was isolated from the mycelial solid cultures of Geotrichum candidum. Its structure was elucidated by spectroscopic methods. The antifungal activity of the new compound against Peronophythora litchii was assessed by microplate Alamar blue assay (MABA).
文摘Cyclocarbon fully consists of sp-hybridized carbon atoms,which shows quite unusual electronic and geometric structures compared to common molecules.In this work,we systematically studied strain energy(SE)of cyclocarbons of different sizes using regression analysis method based on electronic energies evaluated at the very accurate DLPNO-CCSD(T)/ccp VTZ theoretical level.In addition,ring strain of two systems closely related to cyclocarbon,boron nitride(BN)ring,and cyclic polyacetylene(c-PA),is also explored.Very ideal relationships between SE and number of repeat units(n)are built for cyclo[2n]carbon,B_(n)N_(n),and[2n]c-PA as SE=555.0·n^(-1),145.1·n^(-1),and 629.8·n^(-1)kcal·mol^(-1),respectively,and the underlying reasons of the difference and similarity in their SEs are discussed from electronic structure perspective.In addition,force constant of harmonic potential of C-C-C angles in cyclocarbon is derived based on SE values,the result is found to be 56.23 kcal·mol^(-1)·rad^(-2).The possibility of constructing homodesmotic reactions to calculate SEs of cyclocarbons is also explored in this work,although this method is far less rigorous than the regression analysis method,its result is qualitatively correct and has the advantage of much lower computational cost.In addition,comparisons show thatωB97XD/def2-TZVP is a good inexpensive alternative to the DLPNO-CCSD(T)/cc-p VTZ for evaluating energies used in deriving SE,while the popular and very cheap B3LYP/6-31G(d)level should be used with caution for systems with global electron conjugation such as c-PA.
基金Financial support by the National Natural Science Foundation of China and by the Special Funds for Major State Basic Research Projects(G1999064800)is gratefully acknowledged.
文摘Treatment of 1,3-di- t -butylcyclopentadiene with rhodium trichloride in EtOH leads to the formation of binuclear half-sandwich complex [Cp t RhCl( μ -Cl)] 2 (1) (Cp t = η 5- t Bu 2C 5H 3) which reacts with trimethylphosphine to give Cp t Rh(PMe 3)Cl 2(2) in high yield. 2 reacts with ammonium polysulfide, (NH 4) 2S x to give cyclooligosulfido half-sandwich complexes Cp t Rh(PMe 3)(S n )( n =4(4a),6(4b)). Desulfurization of 4b by excess PPh 3 results in cyclotetrasulfido product 4a, while 4a takes up sulfur from polysulfide to convert cyclohexasulfido product 4b. The reaction of 2 with Et 4NI gives diiodide complex 3 which is determined by single crystal X-ray crystallographic analysis.
