热作用对肾组织光传输特性的影响

研究了热作用下的肾组织对532 nm和1064 nm波长的光学特性的影响。实验利用带积分球附件的分光光度计和采用反向倍增法获取组织的光学特性,结果表明热作用下的肾组织对532 nm和1 064 nm的吸收系数和约化散射系数都是随着加热温度的变化而变化的。在25℃到80℃的温度范围内,肾组织对532 nm的吸收系数和约化散射系数都分别显著地较其对1064 nm的吸收系数和约化散射系数要大。其对532 nm和1 064 nm的吸收系数的最大值都在80℃,其值分别为1.121 mm-1和0.269 mm-1,最小值都在25℃,其值分别为0.131 mm-1和0.019 mm-1。其对532 nm和1 064 nm的约化散射系数的最大值分别在80℃和70℃,其值分别为2.905 mm-1和0.705 mm-1,最小值都在25℃,其值分别为0.391 mm-1和0.184 mm-1。研究结果提示,热作用的温度是影响肾组织的吸收和散射特性的重要因素。     

肾组织脱水对组织光学吸收和散射特性的影响

研究肾组织脱水对组织的吸收和散射特性的影响,实验利用带积分球附件的分光光度计和采用反向倍增法获取组织对532 nm和1064 nm波长的吸收和散射特性。结果表明:在37℃下脱水的肾组织对532 nm和1064 nm的吸收系数和约化散射系数都是随着脱水率的增大而明显地增大的,在37℃下脱水的肾组织对532 nm和1064 nm的吸收系数均明显地较自然的肾组织对相应波长的吸收系数要大,而在37℃下脱水的肾组织对532 nm和1064 nm的约化散射系数也明显地较自然的肾组织对相应波长的约化散射系数要大,在相同脱水率下的肾组织对于532 nm的吸收系数和约化散射系数都明显地较其对1064 nm的吸收系数和约化散射系数要大。研究结果提示,组织脱水、脱水的温度和脱水时间是影响肾组织的吸收和散射特性的重要因素。     

自然和热凝固的人肝组织对KTP/YAG激光的光学特性的比较研究

本文采用双积分球测量系统和Inverse Add ing-Doub ling方法,研究了自然和热凝固的人肝组织对532nm的KTP激光和1 064 nm的Nd:YAG激光的光学特性。结果表明:热凝固的人肝组织对532 nm的KTP激光的吸收系数较自然的肝组织的吸收系数增大了23.5%(P<0.05),热凝固的肝组织对1 064 nm的Nd:YAG激光的吸收系数较自然的肝组织的吸收系数减小了34.3%(P<0.05)。热凝固的人肝组织对532 nm的KTP激光的散射系数较自然的肝组织的散射系数增大了4.50倍(P<0.05),热凝固的肝组织对1 064 nm的Nd:YAG激光的散射系数较自然的肝组织的散射系数增大了6.41倍(P<0.05)。热凝固的人肝组织对532 nm的KTP激光的各向异性因子较自然的肝组织的各向异性因子减小了5.47%,热凝固的肝组织对1 064 nm的Nd:YAG激光的各向异性因子较自然的肝组织的各向异性因子减小了1.95%。     

采用不同的光传输模型比较研究结肠的散射和吸收特性:离体结肠肿瘤的光学诊断

测定和比较研究了离体的正常的和腺癌的人结肠粘膜/粘膜下层以及正常的和腺癌的人结肠肌层/浆膜组织对630 nm,680 nm,720 nm,780 nm,810 nm,850 nm和890 nm波长的钛宝石激光的散射和吸收系数。采用双积分球测量系统测量组织样品对七个不同波长的激光的准直透射、漫反射和漫透射,从实验所测结果以及分别采用反向倍增法和反演蒙特卡罗技术这两个光学模型计算出组织的散射和吸收系数。研究结果表明,无论是用反向倍增法还是用反演蒙特卡罗法,每一种类型的正常的和腺癌的人结肠组织对同一波长的激光的吸收系数和散射系数有显著性的差异(P<0.01),正常的和腺癌的结肠组织的散射和吸收系数有大的差异,这些结果提示每种类型的正常和腺癌的结肠组织的组份和结构之间有大的差异。四种类型的结肠组织对七个不同波长的激光的散射系数较其吸收系数至少要大三个数量级,而四种类型的结肠组织对七个不同波长的激光的散射系数有相同的数量级。     

用组织光学特性鉴别诊断人离体的正常膀胱和膀胱癌组织

研究正常人膀胱和膀胱癌组织在Kube lka-Munk二流模型下对476.5 nm,514.5 nm和808 nm波长的激光的光学特性的差异。采用双积分球系统和Kube lka-Munk二流模型进行测量研究。实验结果表明,正常膀胱和膀胱癌组织在Kube lka-Munk二流模型下对476.5 nm,514.5 nm和808 nm波长的每一个波长的激光的吸收、散射、总衰减、有效衰减系数都有非常显著性的差异(P<0.01)。膀胱癌组织对476.5 nm,514.5 nm和808nm波长的激光的吸收系数明显地较正常膀胱组织对相应波长的激光的吸收系数要大(P<0.01),膀胱癌组织对476.5 nm和514.5 nm波长的激光的散射系数明显地较正常膀胱组织对相应波长的激光的散射系数要小(P<0.01),而膀胱癌组织对808 nm波长的激光的散射系数明显地较正常膀胱组织对同一波长的激光的散射系数要大(P<0.01)。膀胱癌组织对476.5 nm,514.5 nm和808 nm波长的激光的总衰减系数明显地较正常膀胱组织对相应波长的激光的总衰减系数要大(P<0.01),膀胱癌组织对476.5 nm,514.5 nm和808 nm波长的激光的有效衰减系数明显地较正常膀胱组织对相应波长的激光的有效衰减系数要大(P<0.01)。提示使用双积分球系统和Kube lka-Munk二流模型来确定离体的正常膀胱组织和膀胱癌组织对476.5 nm,514.5 nm和808nm波长的激光的光学特性的差异鉴别诊断病变的膀胱组织是一个有效的方法。     

无损光学法测量人胃粘膜/粘膜下层组织的光衰减特性

研究了人正常胃粘膜及粘膜下层组织对640 nm,690 nm,740 nm,790 nm,840 nm和890 nm波长的钛宝石激光的光衰减特性以及光学穿透深度,实验采用激光斜入射式空间分辨反射光和CCD探测器以及非线性拟合确定组织光学特性。结果表明:人正常胃粘膜及粘膜下层组织对六个波长的激光的有效衰减系数和光学穿透深度都是随着激光波长的变化而变化的。其有效衰减系数的最大值在640 nm,其值为1.12 mm-1,最小值在790 nm,其值为0.901 mm-1,最大差异在790 nm和890 nm之间,其值为19.9%,最小差异在690 nm和740nm之间,其值为2.83%。其光学穿透深度的最大值在790 nm,其值为1.11 mm,最小值在640 nm,其值为0.890 mm,最大差异在640 nm和790 nm之间,其值为24.7%,最小差异在690 nm和740 nm之间,其值为2.97%。     

用蒙特卡罗方法模拟光在多层组织中的吸收特性

在讨论目前新颖的组织功能成像打骂能性（例如光声成像）时,光子在组织中的吸收和散射特性是一个很重要的问题,鉴于这一点,本文利用一个多层模型研究了光子在皮肤,脂肪和肌肉组织中的吸收和散射特性,得到了在组织中某一深度处光子在一个平面上的吸收分布,以及在不同吸收系数和散射系数的情况下,光子的反射,吸收和透射几率,结果表明在经过多次散射后,大部分的光子被吸收,在本文的模型中只有7.3%的光子从表面反射（包括镜面反射和漫反射）,还讨论了不同光学参灵敏对参流分布的影响。     

Kubelka—Munk模型下的兔血管对He—Cd激光的散射与吸收特性

测量了兔动脉和静脉夺He-Cd激光的反射和透射传输特性。实验采用两积分球系统及波长为441.6nm的He-Cd激光器,并根据测量数据及采用Kubelka-Munk模型分析和计算了兔动脉和静脉组织对该波长激光的吸收系统、散射系数及总的光强I（x）及前向散射通量i(x)和后向散射通量j(x）随厚度的变化情况。结果表明,兔动脉和静脉的温反射率和透射率有明显差别,而且,动脉对激光的吸收系数明显较静脉的要小,耐动脉对激光的散射系数却明显较静脉的要大,在动脉和静脉组织中总的光强I(x)及前向散射通量i(x)和后向散射通量j(x)随厚度的变化情况也有明显的区别。     

光学成像中兼具光学和力学性质的生物组织仿体

在生物医学光学成像方法的研发、评估和使用中,需要用到在较长时间内具有稳定的光学及力学属性的生物组织仿体,以使光学成像实验可以重复进行。这些仿体一般由混有散射、吸收粒子的基质制成。常用散射粒子包括脂质微粒、聚合物微球、金属氧化物粉末和金纳米粒子等,吸收粒子(及其溶液)包括血液、印度墨水(Indian Ink)和分子染料等。常用来模拟组织特性的基质包括硅胶、纤维蛋白和聚乙烯醇凝胶(Polyvinyl alcohol cryogel,PVA-C)等。讨论和分析常见仿体的光学性质(吸收系数、散射系数、折射率)和力学性质(弹性和粘弹性)。从生物相容性、制备难易程度及耗时情况、稳定性等方面比较了几种常见散射粒子、吸收粒子和基质的优缺点,并据此总结其适用范围。最后对仿体研究的发展进行了展望。     

时间分辨反射确定生物组织光学性质的方法研究

通过考虑吸收系数对漫射常数的影响,改进了时间分辨反射中两点测量生物组织光学性质的方法,对约化散射系数与吸收系数之比较小的生物组织进行了模型测量,结果表明此种不仅减小了测量的系统误差,而且扩展了两点测量法的应用范围。同时也较为详细地讨论了有效时间的选择和光源与探测点间的距离对测量结果的影响。     

The first structural study on a cyclic tricoordinate phosphorochloridite and a pentacoordinate phosphorane based on 1,2,3,5-protected myo-inositol--a new conformation of 1,3,2-dioxaphosphorinane ring

Treatment of the phosphoramidite [myo-C(6)H(6)-2-[OC(O)Ph]-1,3,5-(O(3)CH)-4,6-(O(2)P-NH-i-Pr)] with o-chloranil affords the first example of inositol-based pentacoordinate phosphorane [myo-C(6)H(6)-2-[OC(O)Ph]-1,3,5-(O(3)CH)-4,6-(O(2)P-NH-i-Pr)(1,2-O(2)C(6)Cl(4))] (9) (X-ray structure) with a trigonal bipyramidal geometry at phosphorus. The six-membered 1,3,2-dioxaphosphorinane ring with the inositol residue has an unusual boat conformation in 9 which is quite different from that found in unrestrained rings investigated before, but is similar to that of its P(III) chloro precursor [myo-C(6)H(6)-2-[OC(O)Ph]-1,3,5-(O(3)CH)-4,6-(O(2)PCl)] (X-ray structure). Also, a convenient and chromatography-free procedure for the protected myo-inositol derivative [myo-C(6)H(6)-2-[OC(O)Ph]-1,3,5-(O(3)CH)-4,6-(OH)(2)] is reported.     

Addition of a peptide fragment on an alpha-helical depsipeptide induces alpha/3(10)-conjugated helix: synthesis, crystal structure, and CD spectra of Boc-Leu-Leu-Ala-(Leu-Leu-Lac)3-Leu-Leu-OEt

The depsipeptide Boc(1)-Leu(2)-Leu(3)-Ala(4)-Leu(5)-Leu(6)-Lac(7)-Leu(8)-Leu(9)-Lac(10)-Leu(11)-Leu(12)-Lac(13)-Leu(14)-Leu(15)-OEt(16) (1) (Boc = tert-butyloxycarbonyl, Lac = L-lactic acid residue) has been synthesized from the peptide Boc-Leu-Leu-Ala-OEt (2) and a depsipeptide, Boc-(Leu-Leu-Lac)(3)-Leu-Leu-OEt (3). Single crystals of 1 were successfully obtained and the structure has been solved by direct methods (such as Sir2002 and Shake-and-Bake). Interestingly, 1 adopts an alpha/3(10)-conjugated helix containing a kink at the junction of peptide and depsipeptide segments, Leu3-Lac7. This is significantly different from the conformation of 3, which has a straight alpha-helical structure with standard phi and psi angles. Microcrystalline CD spectra were also studied to compare structural properties of 1 and 3. The differences between alpha/3(10)- and alpha-helices appear in these CD spectra.     

Single diastereomers of unsymmetrical tris-spirocyclic cyclotriphosphazenes based on 1,1'-bi-2-naphthol--synthesis and structures

Diastereoselective synthesis and characterization of chiral unsymmetrical tris-spirocyclic cyclotriphosphazenes based on chiral 1,1'-bi-2-naphthol (BINOL) are reported. Specifically, the chiral compounds (-)N(3)P(3)[1,1'-O(2)(C(10)H(6))(2)](O-2,2'C(6)H(4)-C(6)H(4)O)Cl(2) [(-)-4] and (-)N(3)P(3)[1,1'-O(2)(C(10)H(6))(2)](OCH(2)CH(2)NMe)(2) [(-)-5] are prepared by starting with the chiral mono-spiro compound (-)N(3)P(3)[1,1'-O(2)(C(10)H(6))(2)]Cl(4) [(-)-3]. Synthesis of four other chiral spirocyclics, N(3)P(3)[1,1'-O(2)(C(10)H(6))(2)](OCH(2)CH(2) NMe)(O-2,2'C(6)H(4)-C(6)H(4)O)[(-)-6 and (+)-6], N(3)P(3)[1,1'-O(2)(C(10)H(6))(2)](NMe(2))(4) [(-)-7], N(3)P(3)[1,1'-O(2)(C(10)H(6))(2)](O-2,2'C(6)H(4)-C(6)H(4)O)(NMeCH(2)CH(2)OH)(2) [(-)-8 and (+)-8], and N(3)P(3)[1,1'-O(2)(C(10)H(6))(2)](O-2,2'C(6)H(4)-C(6)H(4)O)[NHCH(2)CH(2)CH(2)Si(OEt)(3)](2) (9) is also reported herein. Compounds 4-6 are obtained in the solid state diastereoselectively and their X-ray structures have been determined and discussed. The diastereoselectivity is also shown by structural characterization of two distinct isomers in the case of 6 [(-)-6 and (+)-6, respectively] by starting with precursor of 3 having (R) or (S)-BINOL residue. The (1)H NMR spectra of 7 and 8 exhibit doublets with virtual coupling for the methyl protons, consistent with the chiral nature of the binaphthoxy residue. The potential of 9, which hydrolyzes readily in CDCl(3) solution, as a useful precursor for chiral polymer applications is highlighted.     

Highly efficient synthesis of alternate alpha- and beta-(1-->3)-linked glucose hepta- and octasaccharides

Two heptasaccharides alpha-D-Glcp-(1-->3)-beta-D-Glcp-(1-->3)-alpha-D-Glcp-(1-->3)-beta-D-Glcp-(1-->3)-alpha-D-Glcp-(1-->3)-beta-D-Glcp-(1-->3)-beta-D-Glcp-1-OMP and beta-D-Glcp-(1-->3)-alpha-D-Glcp-(1-->3)-beta-D-Glcp-(1-->3)-alpha-D-Glcp-(1-->3)-beta-D-Glcp-(1-->3)-alpha-D-Glcp-(1-->3)-beta-D-Glcp1-OMP, and two octasaccharides alpha-D-Glcp-(1-->3)-beta-D-Glcp-(1-->3)-alpha-D-Glcp-(1-->3)-beta-D-Glcp-(1-->3)-alpha-D-Glcp-(1-->3)-beta-D-Glcp-(1-->3)-alpha-D-Glcp-(1-->3)-beta-D-Glcp-1-OMP and beta-D-Glcp-(1-->3)-alpha-D-Glcp-(1-->3)-beta-D-Glcp-(1-->3)-alpha-D-Glcp-(1-->3)-beta-D-Glcp-(1-->3)-alpha-D-Glcp-(1-->3)-beta-D-Glcp-(1-->3)-beta-D-Glcp1-OMP were synthesized in a stereospecific way by remote control.     

Cyclopeptides from Sagina japonica (Caryophyllaceae)

Two new cyclic peptides, named sajaponicin C (1) and sajaponicin D (2), were isolated from the whole plants of Sagina japonica (Caryophyllaceae). Their structures were determined as cyclo(Pro(2)-Leu(2)-Tyr-Leu(1)-Phe(1)-Pro(3)-Phe(2)-Pro(1)) (1) and cyclo(Pro(1)-Pro(2)-Pro(3)-Pro(4)-Phe(1)-Gly-Thr-Ser-Phe(2)-Ile-Tyr) (2) on the basis of spectroscopic data, especially by two-dimensional (2D) NMR techniques.     

Enantioselective recognition of ammonium perchlorate salts by optically active monoaza-15-crown-5 ethers

Chiral monoaza-15-crown-5 ethers (1, 2) were prepared from (R)-(-)-2-amino-1-butanol in high yield. The chiral monoaza-15-crown-5 ethers were purified directly as NaClO(4) complexes. Molecular recognition by these chiral monoaza-crown ethers of (R)- and (S)-PhEtHClO(4) and (R)- and (S)-NapEtHClO(4) as characterized by UV-vis spectroscopy. The order of enantiomeric selectivity is (R)- > (S)- PhEtHClO(4) and (S)- > (R)-NapEtHClO(4) for 1. In the case of 2 it was (R)- > (S)-PhEtHClO(4) and (R)- > (S)- NapEtHClO(4). The cavity of macrocycle and steric hindrance of the benzene units appears to play an important role in recognition.     

Efficient adenylyl cyclase activation by a beta2-adrenoceptor-G(i)alpha2 fusion protein

The G-protein G(i)alpha can activate adenylyl cyclase (AC), but the relevance of this AC activation is unknown. We used receptor-G protein co-expression and receptor-G protein fusion proteins to investigate G(i)alpha(2) regulation of AC in Sf9 cells. G(i)alpha(2) was fused to the beta(2)-adrenoceptor (beta(2)AR), a preferentially G(s)-coupled receptor, or the formyl peptide receptor (FPR), a G(i)-coupled receptor. The FPR co-expressed with, or fused to, G(i)alpha(2), reduced AC activity. In contrast, the beta(2)AR fused to G(i)alpha(2) was a highly efficient AC activator, while the beta(2)AR co-expressed with G(i)alpha(2) was not. Agonist efficiently stimulated incorporation of [alpha-32P]GTP azidoanilide into beta(2)AR-G(i)alpha(2). We explain AC activation by beta(2)AR-G(i)alpha(2) by a model in which there is interaction of the beta(2)AR and AC, preventing tethered G(i)alpha(2) from interacting with the inhibitory G(i)alpha site of AC. The postulated beta(2)AR/AC interaction brings G(i)alpha(2) into close proximity of the G(s)alpha site of AC, enabling G(i)alpha(2) to activate AC.     

3-Amidoquinuclidine derivatives: synthesis of compounds and inhibition of butyrylcholinesterase

The synthesis of racemic and enantiomerically pure 3-butanamidoquinuclidines ((+/-)-Bu, (R)-Bu and (S)-Bu), (1-3) and 3-benzamidoquinuclidines ((+/-)-Bz, (R)-Bz, and (S)-Bz), (4-6) is described. The N-quaternary derivatives, N-benzyl-3-butanamidoquinuclidinium bromides ((+/-)-BnlBu, (R)-BnlBu and (S)-BnlBu), (7-9) and N-benzyl-3-benzamidoquinuclidinium bromides ((+/-)-BnlBz, (R)-BnlBz and (S)-BnlBz), (10-12) were subsequently synthesized. The interaction of the four enantiomerically pure quaternary derivatives with horse serum butyrylcholinesterase (BChE) was tested. All tested compounds inhibited the enzyme. The best inhibitior of the enzyme was (S)-BnlBz with a K(i) = 3.7 microM. The inhibitor potency decreases in order (S)-BnlBz > (R)-BnlBz > (R)-BnlBu > (S)-BnlBu.