Investigation of Bimetallic Nickel Catalysts in Catalyst‐Transfer Polymerization of π‐Conjugated Polymers

A comparative study involving bimetallic nickel catalysts designed from disubstituted N,N,N′,N′‐tetra(diphenylphosphanylmethyl)benzene diamine bridging ligands is reported. Catalyst behavior is explored in the Kumada catalyst‐transfer polymerization (KCTP) using poly(3‐hexylthiophene) (P3HT) as the model system. The success of a controlled polymerization is monitored by analyzing monomer conversion, degree of polymerization, end‐group identity, and molecular weight distribution. The characterization of P3HT obtained from KCTP initiated with the bimetallic catalysts shows chain‐growth behavior; however, the presence of Br/Br end‐groups and broader molecular weight distribution reveals a reduced controlled polymerization compared to the commonly employed Ni(dppp)Cl₂. The observed increase in intermolecular chain transfer and termination processes in KCTP initiation with the bimetallic catalysts can be attributed to a weaker Ni(0)‐π‐aryl complex interaction, which is caused by increased steric crowding of the coordination sphere.     

Direct Observation of a Cyclic Vinyl Polymer Prepared by Anionic Polymerization using N‐Heterocyclic Carbene and Subsequent Ring‐Closure without Highly Diluted Conditions

A 1:1 adduct of methyl sorbate (MS) and 1,3‐di‐tert‐butylimidazol‐2‐ylidene (NHCtBu) initiates anionic polymerization of a nonconjugated polar alkene, allyl methacrylate (AMA) in toluene at ?20 °C. After the monomer is consumed quantitatively using a bulky aluminum Lewis acid, methylaluminum bis(2,6‐di‐tert‐butyl‐4‐methylphenoxide) (MAD), as an additive, successive ring‐closure occurs without highly dilute conditions to give a cyclic poly(AMA) containing α‐terminal MS unit, and an M_n of 8.8 × 10³?58.5 × 10³ with a narrow molecular dispersity index (M_w/M_n = 1.1₄–1.3₇). The lack of a need for dilution is due to the fact that an α‐terminal NHCtBu group is acting as the counter cation for the propagating center in the polymerization. From ¹H NMR and matrix assisted laser desorption/ionization (MALDI‐TOF) mass spectra, combined with transmittance electron microscope (TEM) observation of a synthesized poly(AMA) with longer alkyl side chains prepared via a thiol‐ene click reaction, it is concluded that once the monomer is consumed, nucleophilic attack at the neighboring methine of the α‐terminal NHCtBu residue by the propagating anionic center causes ring‐closing to cyclic poly(AMA).     

应用可吸收钉棒治疗关节内骨折

目的探讨可吸收钉、棒治疗关节内骨折的效果。方法1998年6月～2004年8月，应用自身增强一聚乙酯（self-reinforced polyglycolic acid，SR—PGA）、自身增强一聚丙酯（self—reinforced poly—L—Lacticacid，SR—PLLA）可吸收螺钉、棒，手术治疗关节内骨折35例，其中男30例，女5例。年龄4～62岁。均为关节内或关节周围松质骨骨折。手术时间为伤后3h～29d。应用SR—PGA全螺纹钉9枚，SR—PLLA拉力螺钉26枚，SR—PLLA固定棒15枚。术后行骨牵引或石膏外固定。结果患者术后获随访3～60个月，平均28个月，伤口均Ⅰ期愈合；骨折于1～3个月内达临床愈合，无再移位、感染及局部积液。患者关节功能恢复满意。根据美国骨科协会（AASO）关节功能评价：优26例，良7例，可1例，差1例，优良率94．3％。结论可吸收内固定钉、棒治疗关节内及关节周围骨折，免除了患者二次手术取出内固定物的痛苦，是一种有效和较为理想的方法。     

自增强可吸收内固定治疗儿童肘部骨折

目的评价自增强可吸收内固定治疗儿童肘部骨折的可行性和有效性。方法2002年7月-2003年12月，25例儿童肘部骨折应用自增强可吸收内固定螺钉或棒固定，对其手术方法、骨折愈合、功能恢复进行回顾性分析总结。结果平均随访时间18个月（10-24个月）。所有骨折均于4周内达到临床愈合。1例肱骨髁上骨折因可吸收棒穿于皮下引起疼痛，妨碍关节活动，于术后6周拔除，恢复良好。1例肱骨内上髁骨折予可吸收螺钉固定，为保持骨折复位稳定，术后伸肘位石膏固定3周致关节僵硬，经CPM被动活动锻炼后肘关节活动基本恢复正常。其余病例在最后一次随访时，均关节活动良好，无畸形发生，也未见局部无菌性反应。结论自增强可吸收内固定治疗儿童肘部骨折可靠有效，近期随访效果满意，术后可早期进行功能锻炼。     

关节镜下可吸收性半月板箭治疗半月板损伤的初步报告

目的关节镜下应用可吸收性半月板箭治疗半月板损伤并评价其近期疗效。方法2002年2～10月,关节镜下采用半月板箭缝合固定12例12侧半月板损伤,男5例,女7例;年龄18～58岁,平均33.2岁。左膝4例,右膝8例。内侧半月板损伤4例,外侧半月板损伤8例;前角损伤2例,体部损伤3例,后角损伤7例。红区损伤10例,红-白区损伤2例。病程3d～5个月,平均2.3个月,其中急性损伤(病程<1个月)9例。关节镜下采用新型全内半月板箭技术固定,共使用25枚半月板箭(平均每例2.1枚)。5例同时施行其它类型手术。结果所有病例术后均无早期并发症发生。全部患者均获得随访,随访时间7～13个月,平均10.2个月。随访时所有患者膝关节稳定,无疼痛、绞锁等症状,6周后关节活动度全面恢复。Lysholm评分由术前的平均(45.6±13.4)分增加到术后平均(82.4±16.3)分,差异有显著性(P< 0.05)。2例分别于术后8个月和9个月出现关节积液,考虑为滑膜炎,经治疗后消失。结论对于半月板损伤,如撕裂类型和部位适当,可选择可吸收性半月板箭治疗。半月板箭技术是一种简便快捷、安全有效的半月板缝合方法。     

Synthesis,Characterization, and in Vitro Stability of Chitosan-Methotrexate Conjugates

Pharmaceutical Research -     

SCHWANN CELLS AND THE REGROWTH OF AXONS IN THE MAMMALIAN CNS: A REVIEW OF TRANSPLANTATION STUDIES IN THE RAT VISUAL SYSTEM

1. We have used peripheral nerve transplants or cultured Schwann cells grafted in association with different types of polymer to study axonal regrowth in the rat visual system. In some instances the glia were co-grafted with fetal tectal tissue. 2. The studies have two main aims: (i) to determine whether retinal axons can be induced to regrow at a site distant from their cell soma, that is, after damage to the brachial region of the optic tract; (ii) to determine whether retinal axons exposed to Schwann cells retain the ability to recognize their appropriate target neurons in CNS tissue. 3. In brachial lesion studies, Schwann cells were placed in the lesion site in association with nitrocellulose papers, within polycarbonate tubes in the presence or absence of a supporting extracellular matrix (ECM), or within polymer hydrogel scaffolds. Autologous sciatic nerve grafts were also used. Immuno-histochemical studies revealed the presence of regenerating axons within all polymer bridges. Regrowth of retinal axons was also seen, however, growth was not extensive and was limited to the proximal 1–1.5 mm of the implants. 4. In target innervation experiments, two surgical paradigms were developed. In one experiment, a segment of sciatic nerve was autografted onto the transected optic nerve in adult rats and the distal end of each graft was placed adjacent to fetal tectal (target) tissue implanted into the frontal cortex. To date, we have not been able to demonstrate selective recognition of target regions within tectal transplants by retinal axons exiting the sciatic nerve implants. 5. In the second experiment, Schwann cells were mixed with fetal tectal cells and co-grafted to the midbrain of newborn host rats. Schwann cells altered the characteristic pattern of host retinal growth into tectal grafts; in some cases axons were induced to grow away from appropriate target areas by nearby co-grafted Schwann cells. 6. In summary, Schwann cell/polymer scaffolds may provide a useful way of promoting the regrowth of damaged axons in the CNS, however: (i) in adults, at least, their effectiveness is reduced if they are located at a distance from the cell bodies giving rise to regenerating axons; (ii) in some circumstances exposure to a peripheral glial environment may affect the capacity of regenerating axons to recognize appropriate target cells in the CNS neuropil.     

Recurrent locking of knee joint caused by intraarticular migration of bioabsorbable tibial interference screw after arthroscopic ACL reconstruction

Two cases are reported in which, after ACL reconstruction with autologous hamstring grafts, tibial polylactide interference screws migrated into the knee joint. Clinically, both patients presented with recurrent locking of the joint. In one case, a broken 15 mm-long tip of the screw was found intra-articularly. In the other case, the whole screw had migrated into the joint cavity. The degradation process of polylactic acid, operative technique and bone quality are discussed as possible reasons for these complications.     

头孢噻肟钠聚合物测定实验条件的改进

目的:对中国药典收载的头孢噻肟钠聚合物测定条件进行改进。 方法 :采用高效液相色谱法 ,以Sephadex G- 10色谱柱 4 2 cm× 1.3cm对 6批样品进行分析 ,分别进样 5 0μl和 2 0 0μl,按外标法计算聚合物的量。结果:头孢噻肟钠在 10～ 6 0 μg/m l范围内线性关系良好 (r=0 .9995 ) ,高中低浓度的加样回收率分别为 10 0 .2 %、10 0 .4 %、99.7% ;RSD分别为 1.7%、1.5 %、1.9% (n =3)。该方法与药典方法比较 ,差异无统计学意义 (P >0 .0 5 )。 结论:本方法简便、快速、可行 ,具有实用价值     

Calculation of Hydrolytic Rate Constants of Poly(ortho ester)s from Molecular Weights Determined by Gel Permeation Chromatography

Purpose. To obtained rate constants from weight-averaged (M_w) or z-averaged (M_z) molecular weights for polymers of Schule-Flory distribution and undergoing random scission. These constants were compared with those obtained by parallel ¹HNMR studies. Methods. The hydrolysis of two poly(ortho ester)s were followed by ¹HNMR and gel permeation chromatography (GPC). Results. Equations to convert number-averaged (M_n), M_w and M_z into fraction of backbone remaining (f_c) were derived. First-order hydrolytic rate constants of two poly(ortho ester)s; DETOSU-HD and DETOSU-CDM were calculated using these relationships. The rate constants calculated from ¹HNMR, M_z and M_w were 0.215, 0.218 and 0.182 hr^–1, respectively, for DETOSU-CDM and 0.152, 0.086 and 0.038 hr^–l for DETOSU-HD. The large discrepancy in the rates determined by ¹HNMR and GPC in the latter case was attributed to that the detector response (refractive index) of the monomers was lower than that of the high molecular weight polymer. The difference is small in the case of DETOSU-CDM, and the rates calculated from GPC data were comparable or nearly identical to that obtained from ¹HNMR data. Conclusions. Although GPC can yield rapid and valuable kinetic data for the degradation of biodegradable polymers, the system, however, must be carefully calibrated to account for the variations in Mark-Houwink coefficients and in the response of the mass detector between the high and low MW polymers.