4’苯甲酰缩氨基硫脲苯并15－冠－5的合成

在多聚磷酸存在下，将冠醚用苯甲酸酰化，合成了４’－苯甲酰基苯并－１５－冠－５。后者在酸性条件下与氨基硫脲反应，合成了４’－苯甲酰缩氨基硫脲苯并－１５－冠－５。最终产品经ＩＲ、ＭＳ和元素分析鉴定了结构。     

管道法合成N,N‘—双（4’—苯并—15—冠—5基）对苯二甲酰胺

采用对苯二甲酰氯与４‘－氨基苯并－１５－冠－５－通过管道法在无水苯中缩合，制得双型双冠醚Ｎ，Ｎ’－双（４‘－苯并－１５－冠－５基）对苯二甲酰胺。该法反应快速，产率达８８％。     

简法合成4′—巯基苯并—15—冠—5

在室温下用氯磺酸将苯并－１５－氯磺酰化,制备高纯度的４′－氯磺酰基苯并－１５－冠－５,然后用Ｚn／硫酸将氯磺酰基还原,制得较高产率的４′－巯基苯并－１５－冠－５ 。     

4‘—苯甲酰缩氨基硫脲苯并—15—冠—5的合成

报道采用在多聚磷酸中将冠醚酰化的方法，合成了４＇－苯甲酰基并－１５－冠－５，以此为原料，在酸性条件下，在与氨基硫脲作用，合成了４＇－苯酰缩氨基硫脲苯并－１５－冠－５，并对合成产物经ＩＲ、ＭＳ和元素分析鉴定了结构。     

管道法合成N,N′-双(4′-苯并-15-冠-5基)对苯二甲酰胺

采用对苯二甲酰氯与４′－氨基苯并－１５－冠－５通过管道法在无水苯中缩合,制得双（苯并冠醚）型双冠醚Ｎ,Ｎ′－双（４′－苯并－１５－冠－５基）对苯二甲酰胺。该法反应快速,产率达８８％。     

4＇－苯甲酰缩氨基硫脲苯并－15－冠－5的合成

报道采用在多聚磷酸中将冠醚酰化的方法，合成了４＇－苯甲酰基苯并－１５－冠－５，以此为原料，在酸性条件下，与氨基硫脲作用，合成了４＇－苯甲酰缩氨基硫脲苯并－１５－冠－５，并对合成产物经ＩＲ．ＭＳ和元素分析鉴定了结构。     

3—苯基茚满酮—（1）—缩氨基硫脲—5,6—苯并—15—冠—5的合成

报道了在多聚磷酸中冠醚酰化的方法,合成了３－苯基茚满酮－（１）－５,６－苯－１５－冠－５。以此为原料,在酸性条件下,与氨基硫脲作用,合成了３－苯工茚满酮－（１）缩氨基硫脲－５,６－苯并－１５－冠－５。经由ＩＲ,ＭＳ和元素分析仪对合成的两种新物质的结构进行鉴定。     

5—（苯并—15—冠—5）—10,15,20—碘化三（对三甲铵苯基）卟啉铑,钌,钯配合…

合成了一种水溶性的５－（苯并－１５－冠－５ ）－１０，１５，２０－碘化三（对三甲铵苯基）卟啉及其与铑、钌、钯的３种新配合物。进行了元素分析，电子光谱，ＩＲ，ＨＮＭＲ表征和光助还原水放Ｈ２的实验。     

新型冠醚交联壳聚糖的合成

利用壳聚糖C2位上活泼氨基与苯甲醛反应,制得了保护氨基的Schiff碱壳聚糖（简称CTB）;再将合成的带有双活性基团的4,4‘-二溴二苯并18-冠-6冠醚与壳聚糖分子的羟基发生反应,得到二苯并18-冠-6冠醚交联的Schiff碱壳聚糖（简称CTBD）,在酸性条件下使CTBD脱去苯甲醛,制得二苯并18-冠-6冠醚交联壳聚糖（简称CTD）。其主要中间体及产物的结构经红外光谱、质谱、核磁共振动等进行了鉴定。     

5-(苯并-15-冠-5)-10,15,20-碘化三(对三甲铵苯基)卟啉铑、钌、钯配合物的合成

合成了一种水溶性的５－（苯并－１５－冠－５）－１０，１５，２０－碘化三（对三甲铵苯基）卟啉及其与铑、钌、钯的３种新配合物。进行了元素分析、电子光谱、ＩＲ、１ＨＮＭＲ表征和光助还原水放Ｈ２的实验。     

Study of the synthesis of chitosan derivatives containing benzo‐21‐crown‐7 and their adsorption properties for metal ions

Three new chitosan crown ethers, N‐Schiff base‐type chitosan crown ethers (I, III), and N‐secondary amino type chitosan crown ether (II) were prepared. N‐Schiff base‐type chitosan crown ethers (I, III) were synthesized by the reaction of 4′‐formylbenzo‐21‐crown‐7 with chitosan or crosslinked chitosan. N‐Secondary amino type chitosan‐crown ether (II) was prepared through the reaction of N‐Schiff base type chitosan crown ether (I) with sodium brohydride. Their structures were characterized by elemental analysis, infrared spectra analysis, X‐ray diffraction analysis, and solid‐state ¹³C NMR analysis. In the infrared spectra, characteristic peaks of C?N stretch vibration appeared at 1636 cm^?1 for I and 1652 cm^?1 for II; characteristic peaks of N? H stretch vibration appeared at 1570 cm^?1 in II. The X‐ray diffraction analysis showed that the peaks at 2θ = 10° and 28° disappeared in chitosan derivatives I and III, respectively; the peak at 2θ = 10° disappeared and the peak at 2θ = 28° decreased in chitosan‐crown ether II; and the peak at 2θ = 20° decreased in all chitosan derivatives. In the solid‐state ¹³C NMR, characteristic aromatic carbon appeared at 129 ppm in all chitosan derivatives, and the characteristic peaks of carbon in C?N groups appeared at 151 ppm in chitosan crown ethers I and III. The adsorption and selectivity properties of I, II, and III for Pd²⁺, Au³⁺, Pt⁴⁺, Ag⁺, Cu²⁺, and Hg²⁺ were studied. Experimental results showed these adsorbents not only had good adsorption capacities for noble metal ions Pd²⁺, Au³⁺, Pt⁴⁺, and Ag⁺, but also high selectivity for the adsorption of Pd²⁺ with the coexistence of Cu²⁺ and Hg²⁺. Chitosan‐crown ether II only adsorbs Hg²⁺ and does not adsorbs Cu²⁺ in an aqueous system containing Pd²⁺, Cu²⁺, and Hg²⁺. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1886–1891, 2002     

Synthesis and adsorption properties for metal ions of mesocyclic diamine‐grafted chitosan‐crown ether

A new type of grafted chitosan‐crown ether was synthesized using mesocyclic diamine crown ether as the grafting agent. The C2 amino group in chitosan was protected from the reaction between benzaldehyde and chitosan to form N‐benzylidene chitosan (CTB). After reaction with mesocyclic diamine crown ether of the epoxy propane group to give mesocyclic diamine‐N‐benzalidene chitosan (CTBA), the Schiff base was removed in a dilute ethanol hydrochloride solution to obtain chitosan‐crown ether (CTDA). Its structure was confirmed by FTIR spectra analysis and X‐ray diffraction analysis. Its static adsorption properties for Pb(II), Cu(II), Cd(II), and Cr(III) were studied. The experimental results showed that the grafted chitosan‐crown ether has high selectivity for the adsorption of Cu(II) in the presence of Pb(II), Cu(II), and Cd(II) and its adsorption selectivity is better than that of chitosan. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1255–1260, 2000     

Synthesis and adsorption properties for metal ions of crosslinked chitosan acetate crown ethers

Two novel chitosan derivatives—crosslinked chitosan dibenzo‐16‐c‐5 acetate crown ether (CCTS‐1) and crosslinked chitosan 3,5‐di‐tert‐butyl dibenzo‐14‐c‐4 diacetate crown ether (CCTS‐2)—were synthesized by the reaction of crosslinked chitosan with dibenzo‐16‐c‐5 chloracetate crown ether and 3,5‐di‐tert‐butyl dibenzo‐14‐c‐4 dichloracetate crown ether with the intent of forming polymers that could be used in hazardous waste remediation as toxic metal‐binding agents in aqueous environments. Their structures were confirmed with elemental analysis, infrared spectral analysis, and X‐ray diffraction analysis. In the infrared spectra of CCTS‐1 and CCTS‐2, the characteristic peaks of aromatic backbone vibration appeared at 1595 cm⁻¹ and 1500 cm⁻¹; the intensity of the N H and O H stretching vibration in the region of 3150–3200 cm⁻¹ decreased greatly. The X‐ray diffraction analysis showed that the peak at 2θ = 20° decreased greatly in CCTS‐1 and CCTS‐2. The adsorption and selectivity properties of CCTS‐1 and CCTS‐2 for Pb²⁺, Cu²⁺, Cr³⁺, and Ni²⁺ were studied. Experimental results showed that the two crosslinked chitosan derivatives had not only good adsorption capacities for Pb²⁺, Cu²⁺, but also high selectivity for Pb²⁺, Cu²⁺ in the coexistence of Ni²⁺. For aqueous systems containing Pb²⁺, Ni²⁺, or Cu²⁺, Ni²⁺, CCTS‐1 only adsorbed Pb²⁺ or Cu²⁺. For aqueous systems containing Pb²⁺, Cr²⁺ and Ni²⁺, CCTS‐2 had high adsorption and selectivity properties for Pb²⁺. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2069–2074, 1999     

Study on the adsorption properties of novel crown ether crosslinked chitosan for metal ions

We first synthesized N‐benzylidene chitosan (CTB) by the reaction of benzaldehyde with chitosan (CTS). Chitosan‐dibenzo‐18‐crown‐6 crown ether bearing Schiff‐base group (CTBD) and chitosan‐dibenzo‐18‐crown‐6 crown ether (CTSD) were prepared by the reaction of 4,4′‐dibromodibenzo‐18‐crown‐6 crown ether with CTB and CTS, respectively. Their structures were confirmed by Fourier transform infrared spectral analysis and X‐ray powder diffraction analysis. These novel crown ether crosslinked CTSs have space net structures with embedded crown ethers and contain the double structures and properties of CTS and crown ethers. They have stronger complexation with and better selectivity for metal ions than corresponding crown ethers and CTS. Moreover, these novel CTS derivatives can be used to separate and preconcentrate heavy or precious metal ions in aqueous environments. From this practical viewpoint, we studied the adsorption and selectivity properties of CTB, CTBD, and CTSD for Ag⁺, Cu²⁺, Pb²⁺, and Ni²⁺. The experimental results showed that CTBD had better adsorption properties and higher selectivity for metal ions than CTSD. For aqueous systems containing Pb²⁺–Ni²⁺ and Pb²⁺–Cu²⁺, the selectivity coefficients of CTSD and CTBD were K/Ni²⁺ = 24.4 and K/Cu²⁺ = 41.4 and K/Ni²⁺ = 35.5 and K/Cu²⁺ = 55.3, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 29–34, 2002; DOI 10.1002/app.10180     

Chemical modification of chitosan: synthesis and biological activity of new heterocyclic chitosan derivatives

BACKGROUND: Numerous works have been published on the chemical modification of chitosan; this polymer is still being modified, leading to various derivatives with improved properties. In the present study, heterocyclic aldehydes including furan‐2‐carbaldehyde, 5‐methylfuran‐2‐carbaldehyde, 3‐pyridine carboxyaldehyde, benzo[d][1,3]dioxole‐5‐carbaldehyde and 4‐oxo‐4H‐chromene‐3‐carbaldehyde were reacted with chitosan by a reductive alkylation reaction to produce for the first time five new N‐heterocyclic chitosan derivatives to improve the biological activity of chitosan against the most important economic plant pests including fungi and insects, in particular the cotton leafworm Spodoptera littoralis. RESULTS: The chemical structures of the synthesized compounds were confirmed by ¹H NMR spectroscopy and the degree of substitution ranged from 0.30 to 0.43. The fungicidal assessment was investigated in vitro using a mycelia radial growth inhibition technique against soil‐borne pathogenic fungi Fusarium oxysporum and Pythium debaryanum and the rice leaf blast Pyricularia grisea. The results showed that N‐[(5‐methylfuran‐2‐yl)methyl] chitosan was the most active against P. grisea with an EC₅₀ value of 0.919 mg mL^?1 while N‐(benzo[d][1,3]dioxol‐5‐ylmethyl) chitosan and N‐(methyl‐4H‐chromen‐4‐one) chitosan exhibited the most potent fungicidal activity against P. debaryanum and F. oxysporum. An insecticidal bioassay against the larvae of S. littoralis showed that N‐(methyl‐4H‐chromen‐4‐one) chitosan exhibited a significant growth inhibition and antifeedant activity among the synthesized compounds. CONCLUSION: The chemical modification of chitosan molecule with a heterocyclic moiety led to an enhancement in the biological activity against the plant pathogenic fungi F. oxysporum, P. debaryanum and P. grisea and the cotton leafworm insect S. littoralis. Copyright © 2007 Society of Chemical Industry     

Synthesis and evaluation of chitosan aryl azacrown ethers as adsorbents for metal ions

New azacrown ether chitosan derivatives (CTS–OC, CTS–NC) were synthesized by reaction of aryl mesocyclic diamine with the C6 hydroxyl group or C2 amino group in chitosan. Their structures were confirmed by elemental analysis, infrared spectra analysis, and X‐ray diffraction analysis. The adsorption and selectivity properties of the aryl azacrown ethers chitosan derivatives for Hg²⁺, Cd²⁺, Pb²⁺, Ag⁺, and Cr³⁺ were also investigated. The experimental results showed that the two chitosan–azacrown ethers have good adsorption capacity for Pb²⁺, Cd²⁺, and Hg²⁺. The adsorption capacity of CTS–OC are higher than that of CTS–NC for Pb²⁺ and Cd²⁺. The chitosan–azacrown ethers have high selectivity for the adsorption of Pb²⁺ and Hg²⁺ with the coexistence of Cd²⁺. The selectivity properties of CTS–OC are better than those of CTS–NC. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3093–3098, 2000     

3种壳聚糖膜的制备及性能比较

以壳聚糖为原料,采用流延法制备了壳聚糖膜、N-乙酰化壳聚糖膜。采用FTIR、XRD和SEN对3种膜的结构和形貌进行了表征,并比较了3种膜的性能。结果表明,N-乙酰化壳聚糖膜的力学性能和耐酸性能好于其它两种膜。     

Factors Influencing the Antibacterial Activity of Chitosan and Chitosan Modified by Functionalization

The biomedical and therapeutic importance of chitosan and chitosan derivatives is the subject of interdisciplinary research. In this analysis, we intended to consolidate some of the recent discoveries regarding the potential of chitosan and its derivatives to be used for biomedical and other purposes. Why chitosan? Because chitosan is a natural biopolymer that can be obtained from one of the most abundant polysaccharides in nature, which is chitin. Compared to other biopolymers, chitosan presents some advantages, such as accessibility, biocompatibility, biodegradability, and no toxicity, expressing significant antibacterial potential. In addition, through chemical processes, a high number of chitosan derivatives can be obtained with many possibilities for use. The presence of several types of functional groups in the structure of the polymer and the fact that it has cationic properties are determinant for the increased reactive properties of chitosan. We analyzed the intrinsic properties of chitosan in relation to its source: the molecular mass, the degree of deacetylation, and polymerization. We also studied the most important extrinsic factors responsible for different properties of chitosan, such as the type of bacteria on which chitosan is active. In addition, some chitosan derivatives obtained by functionalization and some complexes formed by chitosan with various metallic ions were studied. The present research can be extended in order to analyze many other factors than those mentioned. Further in this paper were discussed the most important factors that influence the antibacterial effect of chitosan and its derivatives. The aim was to demonstrate that the bactericidal effect of chitosan depends on a number of very complex factors, their knowledge being essential to explain the role of each of them for the bactericidal activity of this biopolymer.