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Characteristics and Safety Profiles of a Hydrocolloid Polyester Dressing Incorporated with Herbal Extract: In Vitro, in Vivo and Randomized Clinical Studies. 含草药提取物的水胶体聚酯敷料的特性和安全性概况:体外、体内和随机临床研究
IF 17.7 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-12-01 Epub Date: 2022-09-07 DOI: 10.1177/15347346221123639
Nantaporn Namviriyachote, Sasiwimon Arkatchai, Kittipan Rerkasem, Pornprom Muangman

The polyester dressing containing herbal extract had been used for several years. However, some properties had not been investigated. This study examined three parts including in vitro studies, skin irritation in an animal model, and the pilot clinical study in traumatic wounds. In in vitro studies, six different wound dressings consisted of hydrocolloid polyester containing herbal extract (SI-HERB®), hydrofiber (Aquacel®), hydrocolloid polyester (Urgotul®), soft paraffin gauze (Bactigras®), foam (Mepilex®), and biocellulose (Suprasorb® X + PHMB) dressings were comparatively evaluated in physical properties including the fluid absorption, desorption, and fluid drainage ability. The skin irritation test was examined in a rabbit model using SI-HERB® as a tested group. In a clinical study, traumatic patients with leg wounds were randomly assigned to six wound dressings. The primary outcome was the pain level and the secondary outcomes were non-adherence and peri-wound reaction evaluating score. From the study, Bactigras® had the largest pore size but the total area of pore size per field of it was similar to SI-HERB®. There were no significant differences between SI-HERB®, Urgotul®, and Bactigras® in the percentage of absorption and desorption. No dermatologic effect was found in the animal study. In the irritation test on leg wounds, pain level, and peri-wound reaction in hydrocolloid polyester dressing group were significantly lower compared with Aquacel® and Bactigras®. The polyester dressing had the pain level after removal lower than before application while the Mepilex® and Suprasorb® presented that insignificantly increase the pain level. Erythema could be observed in Bactigras®, Aquacel®, and Suprasorb® but the edema scores were not different. A hydrocolloid polyester dressing containing herbal extract had good drainage ability. No skin irritation was reported. Pain scores, removal ability, and peri-wound reaction were also significantly lower with other types of wound dressings. These results suggested that this dressing be an alternative in wound treatment.

含有草药提取物的聚酯敷料已使用多年。然而,有些特性尚未得到研究。这项研究包括三个部分,包括体外研究、动物模型的皮肤刺激性研究和创伤性伤口的试点临床研究。在体外研究中,对六种不同的伤口敷料进行了比较评估,包括含草药提取物的水胶体聚酯(SI-HERB®)、水纤维(Aquacel®)、水胶体聚酯(Urgotul®)、软石蜡纱布(Bactigras®)、泡沫(Mepilex®)和生物纤维素(Suprasorb® X + PHMB)敷料的物理性质,包括液体吸收、解吸和液体排出能力。以 SI-HERB® 为测试组,在兔子模型中进行了皮肤刺激测试。在一项临床研究中,腿部创伤患者被随机分配到六种伤口敷料。主要结果是疼痛程度,次要结果是不依从性和伤口周围反应评估得分。从研究结果来看,Bactigras® 的孔径最大,但其每场孔径的总面积与 SI-HERB® 相似。SI-HERB®、Urgotul® 和 Bactigras® 在吸收和解吸的百分比上没有明显差异。在动物实验中没有发现皮肤效应。在腿部伤口刺激试验中,水胶体聚酯敷料组的疼痛程度和伤口周围反应明显低于 Aquacel® 和 Bactigras®。聚酯敷料移除后的疼痛程度低于使用前,而 Mepilex® 和 Suprasorb® 的疼痛程度增加不明显。Bactigras®、Aquacel® 和 Suprasorb® 均可观察到红斑,但水肿评分没有差异。含有草药提取物的水胶体聚酯敷料具有良好的引流能力。没有皮肤过敏的报道。其他类型伤口敷料的疼痛评分、清除能力和伤口周围反应也明显较低。这些结果表明,这种敷料可作为伤口治疗的替代品。
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引用次数: 0
Determination of the Effectiveness of Topical Product of Commiphora Mukul Oleo Gum Resin on Dermal Wound Healing: An Experimental Study. 确定诃子木果油胶树脂外用产品对皮肤伤口愈合的效果:一项实验研究。
IF 17.7 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-12-01 Epub Date: 2022-09-15 DOI: 10.1177/15347346221123640
Alireza Malayeri, Zeinab Zaheri Abdevand, Masoud Rashedi, Shokouh Sadat Hamedi, Zahra Basir, Fereshteh Golfakhrabadi

In Persian Medicine, many plants have been used in wound healing for thousands of years, and recent evidence indicates the beneficial effects of plant extracts on healing skin wounds. Commiphora mukul oleo gum resin has been considered for a long time due to its various properties such as milk-enhancing, diuretic, and healing the mouth and larynx wounds. The present study aimed to evaluate the effect of Commiphora mukul oleo gum resin on wound healing in rats. Forty-two albino Wistar rats have randomly divided into six groups: The first group was without treatment, the second group was treated with Eucerin, the third group was treated with phenytoin cream %1, the fourth to sixth groups were treated with Commiphora mukul ointment 2%, 4%, and 8% respectively. Treatment was performed once a day for 14 days, and the wound area was measured daily. At the end of the experiment, blood samples were taken to measure vascular endothelial growth factor (VEGF) and platelet-derived growth factor (PDGF). The histological evaluation and the strength test of the repaired tissue were performed. The results showed that seven days after treatment, the wound area decreased significantly in the groups treated with mukul gum extract compared to the control groups (p0.05). At the end of the experiment, there was no significant difference in wound area reduction between the groups. Commiphora mukul gum extract increased VEGF and significantly improved skin elasticity. The results of this study indicate the Wound healing potential of Commiphora mukul.

在波斯医学中,许多植物被用于伤口愈合已有数千年的历史,最近的证据表明,植物萃取物对愈合皮肤伤口有好处。Commiphora mukul oleo 树胶因其具有催乳、利尿、愈合口腔和喉部伤口等多种功效,长期以来一直被认为具有疗效。本研究的目的是评估 Commiphora mukul 油树胶对大鼠伤口愈合的影响。42 只白化 Wistar 大鼠被随机分为 6 组:第一组不做任何处理,第二组使用优色林,第三组使用苯妥英乳膏(%1),第四至第六组分别使用 2%、4% 和 8%的康乃馨软膏。每天治疗一次,连续14天,每天测量伤口面积。实验结束后,抽取血液样本测定血管内皮生长因子(VEGF)和血小板衍生生长因子(PDGF)。对修复组织进行组织学评估和强度测试。结果显示,治疗七天后,与对照组相比,使用木瓜胶提取物治疗的组的伤口面积明显缩小(P0.05)。实验结束时,各组在伤口面积缩小方面没有明显差异。刺五加树胶提取物能增加血管内皮生长因子,显著改善皮肤弹性。这项研究结果表明了荚蒾的伤口愈合潜力。
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引用次数: 0
Full Diabetic Foot Ulcer Healing and Pain Relief Based on Platelet-Rich-Plasma gel Formulation Treatment and the Involved Pathways. 基于血小板富集血浆凝胶配方治疗的糖尿病足溃疡全面愈合和疼痛缓解及其相关途径
IF 17.7 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-12-01 Epub Date: 2022-07-03 DOI: 10.1177/15347346221109758
Krissia Caroline Leme, Guilherme Martins Neri, Gabriel Gaspar Biscaro, Andreia Afaz Bulgareli, Nelson Duran, Maria Candida Ribeiro Parisi, Ângela Cristina Malheiros Luzo

Diabetic foot ulcer is a severe Diabetic Mellitus-associated complication. It is induced by poor glycemic control, which leads to peripheral neuropathy and vascular diseases. Platelet-rich plasma could be beneficial for healing processes due to its active biomolecules that promotes immunomodulation, angiogenesis, cell proliferation and analgesia.

糖尿病足溃疡是一种严重的糖尿病相关并发症。糖尿病足溃疡是糖尿病相关并发症中的一种,其诱因是血糖控制不佳,导致周围神经病变和血管疾病。富血小板血浆具有活性生物大分子,可促进免疫调节、血管生成、细胞增殖和镇痛,因此有益于愈合过程。
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引用次数: 0
Negative Pressure Wound Therapy Promotes Wound Healing by Inhibiting Inflammation in Diabetic Foot Wounds: A Role for NOD1 Receptor. 负压伤口疗法通过抑制糖尿病足伤口的炎症促进伤口愈合:NOD1 受体的作用。
IF 17.7 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-12-01 Epub Date: 2022-10-11 DOI: 10.1177/15347346221131844
Tao Wang, Longhua Fan, Jianjun Liu, Yue Tao, Xu Li, Xiaojun Wang, Limeng Li

Aims: Diabetic foot results in frequent amputation and quality-of-life reduction in diabetes population. These lesions are featured by a prolonged and exaggerated inflammation with a significant impairment in local bacterial invasion. Negative pressure wound therapy (NPWT) attenuates hyperinflammation in the healing of diabetic foot wounds, but the potential mechanism of NPWT down-regulated inflammatory reaction still remains elusive. This study aims to explore the inflammatory signaling involved in the effect of NPWT on diabetic ulcer. Methods: Thirty patients with diabetic foot ulceration were divided into NPWT group (treated with NPWT, n = 10), NPWT + FK565 group (treated with NPWT combined with FK565 which is NOD1 receptor ligand, n = 10) and control group (n = 10). After two weeks treatment, samples were harvested and analyzed by histochemistry for infiltration of inflammatory cells, immunofluorescence stain for NOD1, western blotting for NOD1, RIP2 (Receptor interacting protein 2), IL-1β, TAK1 (Transforming growth factor-β-activated kinase1), p65 and real time-PCR for expression of NOD1 and RIP2. Results: NPWT could notably accelerate the diabetic wound healing through alleviating inflammatory reaction. The immunofluorescence analysis results revealed that NOD1 was mainly expressed in the cytoplasm and noticeably decreased after the NPWT treatment. And NPWT obviously decreased both the mRNA and protein level of NOD1 and RIP2. Moreover, The protein expression of IL-1β, TAK1 and p65 in the NPWT-group were significant decreased. Conclusion: NPWT effectively promotes wound healing by suppressing the wound inflammation in diabetic foot, which is mediated at least in part by suppression of NOD1 receptor.

目的:糖尿病足经常导致糖尿病患者截肢和生活质量下降。这些病变的特点是炎症持续时间长、程度严重,局部细菌侵袭能力显著下降。伤口负压疗法(NPWT)可减轻糖尿病足伤口愈合过程中的炎症反应,但 NPWT 下调炎症反应的潜在机制仍不明确。本研究旨在探讨 NPWT 对糖尿病溃疡的影响所涉及的炎症信号转导。研究方法将 30 名糖尿病足溃疡患者分为 NPWT 组(使用 NPWT 治疗,n = 10)、NPWT + FK565 组(使用 NPWT 联合 FK565(NOD1 受体配体)治疗,n = 10)和对照组(n = 10)。治疗两周后,采集样本并通过组织化学分析炎症细胞的浸润,免疫荧光染色检测 NOD1,Western 印迹检测 NOD1、RIP2(受体相互作用蛋白 2)、IL-1β、TAK1(转化生长因子-β-活化激酶 1)、p65,以及实时荧光定量 PCR 检测 NOD1 和 RIP2 的表达。结果NPWT 可通过减轻炎症反应显著加速糖尿病伤口愈合。免疫荧光分析结果显示,NOD1 主要在细胞质中表达,NPWT 治疗后其表达明显减少。而 NPWT 则明显降低了 NOD1 和 RIP2 的 mRNA 和蛋白水平。此外,NPWT 组 IL-1β、TAK1 和 p65 的蛋白表达也明显下降。结论NPWT 可有效抑制糖尿病足伤口的炎症反应,从而促进伤口愈合。
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引用次数: 0
Green Synthesis of Silver Nanoparticles from Aqueous Extract of Tinospora crispa Stems Accelerate Wound Healing in Rats. 从鸢尾茎的水提取物中绿色合成银纳米粒子可加速大鼠的伤口愈合。
IF 17.7 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-12-01 Epub Date: 2022-11-03 DOI: 10.1177/15347346221133627
Shokhan Osman Mahmud, Suhayla Hamad Shareef, Ahmed A J Jabbar, Rawaz Rizgar Hassan, Hardy Khalid Jalal, Mahmood Ameen Abdulla

Tinospora crispa has been known as an herbal medicine with many biological activities. The current study evaluates silver nanoparticles in accelerating the rate of wound healing and closure of excision wounds in rats. A novel technique was followed to synthesize nanosilver particles, x-ray diffraction, UV-Vis's spectroscopy, and transition electron microscope were used. Sprague Dawley rats (24) were separated into 4 clusters: vehicle group (G1), treated with Vaseline; positive control (G2), treated with the intrasite gel; Experimental groups (G3 and G4), treated with 175 and 350 ppm silver nanoparticles, respectively, with an excisional wound created on the neck area. Wounds were treated topically twice daily for two weeks and sacrificed on day fifteenth. Histology, immunohistochemistry (expression of Bax and HSP 70 proteins), and Masson Trichrome staining procedures disclose that wounds dressed with silver nanoparticles exhibited wound closure site contained less scar, less inflammatory cells, and more collagen compared vehicle group. The endogenous antioxidant enzymes (SOD and CAT) and TGF-β were significantly increased and lipid peroxidation (MDA) and TNF-α were decreased in wound tissue homogenate dressed with silver nanoparticles compared to the vehicle cluster. Silver nanoparticles suggestively improved cell proliferation and stimulated the rate of wound closure, with less scarring, and more fibroblast.

图形摘要:[公式:见正文]。
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引用次数: 0
Carboxymethyl Cellulose-Based Hydrogel Film Combined with Umbilical Cord Blood Platelet gel as an Innovative Tool for Chronic Wound Management: A Pilot Clinical Study. 羧甲基纤维素水凝胶膜结合脐带血血小板凝胶作为慢性伤口管理的创新工具:试验性临床研究。
IF 17.7 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-12-01 Epub Date: 2022-11-15 DOI: 10.1177/15347346221138189
Ilenia Foffa, Agata Janowska, Marco Fabbri, Paola Losi, Elena Ciabatti, Sabrina Gabbriellini, Francesco Faita, Laura De Rosa, Valentina Dini, Alessandro Mazzoni, Marco Romanelli, Giorgio Soldani

Treatment of chronic leg ulcers remains a major challenge and it is a substantial financial burden on individuals, families, caregivers, and health care system. There is increasing evidence on using of autologous Platelet-rich-plasma in wound repair but limited clinical data are available on the efficacy and safety of the use of umbilical cord blood platelet gel (CBPG). In our pilot study, for the first time, we aimed to evaluated the safety and efficacy of the use of umbilical CBPG combined with a hydrogel dressing in 10 patients with chronic venous ulcers (VU). The protocol consisted of application of umbilical cord blood platelet-rich plasma (PRP) combined with a Carboxymethyl cellulose (CMC)-based hydrogel dressing once a week for 4 weeks. The 80% of patients after 4 weeks of treatment had a significantly decrease in wound size. Moreover, we obtained an improvement in terms of mean Wound Bed Score (WBS), numeric rating scale (NRS) value and the EQ-5D index score. This pilot study showed that the topically therapeutic administration of umbilical CBPG associated with a CMC-based hydrogel dressing has the potential to accelerate the healing of chronic lesions without adverse reaction. However, additional studies with larger sample size and longer follow-up periods are required to confirm our findings.

慢性腿部溃疡的治疗仍然是一项重大挑战,对个人、家庭、护理人员和医疗保健系统造成了巨大的经济负担。越来越多的证据表明,自体血小板-血浆可用于伤口修复,但有关使用脐带血血小板凝胶(CBPG)的有效性和安全性的临床数据却很有限。在我们的试点研究中,我们首次对 10 名慢性静脉溃疡(VU)患者使用脐带血血小板凝胶和水凝胶敷料的安全性和有效性进行了评估。治疗方案包括应用脐带血富血小板血浆(PRP)和基于羧甲基纤维素(CMC)的水凝胶敷料,每周一次,持续 4 周。治疗 4 周后,80% 的患者伤口面积明显缩小。此外,我们还改善了平均伤口床评分(WBS)、数字评分量表(NRS)值和 EQ-5D 指数评分。这项试验研究表明,脐带 CBPG 与 CMC 水凝胶敷料的局部治疗用药有可能加速慢性损伤的愈合,且不会产生不良反应。然而,要证实我们的研究结果,还需要更多样本量更大、随访时间更长的研究。
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引用次数: 0
Clinical Efficacy of a 3D Foot Scanner app for the Fitting of Therapeutic Footwear in Persons with Diabetes in Remission: A Randomized and Controlled Clinical Trial. 三维足部扫描仪应用在糖尿病缓解期患者治疗性鞋类装配中的临床疗效:随机对照临床试验。
IF 17.7 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-12-01 Epub Date: 2022-09-06 DOI: 10.1177/15347346221124645
Mateo López-Moral, Raúl J Molines-Barroso, Yolanda García-Álvarez, Francisco J Álvaro-Afonso, Marta García-Madrid, José Luis Lázaro-Martínez

To evaluate the ability of high-risk patients with diabetes in remission to select proper therapeutic footwear (TF) and validate a novel 3D foot scanner app for selecting the proper fitting TF. We conducted a randomized and controlled clinical trial enrolling 30 patients with a previously healed diabetic foot ulcer carried out in a specialized diabetic foot unit between November 2021 and June 2022. All patients were recommended to TF with extra depth volume and rocker sole. The control group could acquire the TF size and model according to aesthetic preferences, while the experimental group had to acquire a specific size and model according to the result of a novel mobile app 3D feet scan. TF was recommended to change when the ill-fitting reasons were found, excessive length or tightness or compromise with toes. The primary outcome measure was the requirement of TF change after prescription because of ill-fitting. A total of seven patients required TF change, one of them (6.7%) in the experimental group and six patients (40%) in the control group (p = .031, 95% CI [0.011-1.04]). Reasons for ill-fitting were as follows: four patients due to excessive length and three patients due to toe compromise. The relative risk reduction for the need to change the TF via the foot scan compared to the control group was 83%, and the number needed to treat was 20. High-risk patients with diabetes tend to select TF with inadequate fitting (length or capacity), and they should be guided hand to hand to acquire proper TF.

目的:评估缓解期糖尿病高危患者选择合适治疗鞋(TF)的能力,并验证用于选择合适治疗鞋的新型 3D 足部扫描仪应用程序。2021 年 11 月至 2022 年 6 月期间,我们在一家糖尿病足专科医院开展了一项随机对照临床试验,共招募了 30 名糖尿病足溃疡愈合患者。所有患者均被推荐使用具有超深容积和摇摆鞋底的 TF。对照组可根据审美偏好选择 TF 的尺寸和型号,而实验组则必须根据新型手机应用 3D 足部扫描的结果选择特定的尺寸和型号。如果发现 TF 不合适、过长、过紧或与脚趾不协调,则建议更换。主要结果指标是处方后因不合适而需要更换 TF 的情况。共有七名患者需要更换 TF,其中实验组有一名患者(6.7%),对照组有六名患者(40%)(P = 0.031,95% CI [0.011-1.04])。不合适的原因如下:4 名患者是因为长度过长,3 名患者是因为脚趾受损。与对照组相比,通过足部扫描需要更换 TF 的相对风险降低了 83%,需要治疗的人数为 20 人。糖尿病高危患者往往会选择不合适的 TF(长度或容量),因此应手把手地指导他们获得合适的 TF。
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引用次数: 0
Confined Assembly Chemistry within Single-Walled Carbon Nanotubes. 单壁碳纳米管的受限组装化学。
IF 18.3 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-11-29 DOI: 10.1021/acs.accounts.5c00661
Yulong Jiang,Bowen Li,Chen Xu,Feng Yang
ConspectusReducing bulk crystals to single-unit chains generally yields unique structures and properties, such as the simplest periodicity, high surface-to-volume ratios, and quantum confinement effects, but their synthesis and stabilization under working conditions remain challenging. Single-walled carbon nanotubes (SWCNTs), with well-defined 1-2 nm channels, provide an ideal platform for confined synthesis and studying atomic-scale molecular transport. Additionally, the conductive single-atomic-layer graphene enables the transmission of properties of substances across monolayer graphene, thus enabling surface property modulation and application. Solution-phase confined assembly in SWCNTs presents a versatile alternative to high-temperature vapor transport that is applicable only when the guests are thermally stable and sublimated, although it is rarely achieved. Unveiling molecular transport at the nanoscale is crucial for an in-depth understanding of the driving forces for assembly and, in turn, controlling confined crystallization of metastable crystals with tailored properties. This Account summarizes our recent progress in liquid-phase confined assembly: (i) assembly methodology and mechanistic insights; (ii) controlled synthesis of one-dimensional (1D) metastable crystals and chains; (iii) emerging properties and applications of single-unit-cell chains. In the end, we summarize the present achievements and future challenges.We employ SWCNTs and atomically precise clusters as models to study liquid-phase confined assembly and its mechanism from a real-space perspective. We developed a scalable solution-phase strategy for assembling diverse clusters within SWCNTs, irrespective of their electronic properties or solubility, which was driven by nanoconfinement and electrostatic interactions. Advanced electron microscopy combined with synchrotron X-ray absorption spectroscopy revealed close-packed ordered single-cluster chains, rather than disordered aggregates, within SWCNTs. Inspired by the confined assembly phenomena, we demonstrated efficient capture of heavy elements, including uranium and iodine, within SWCNTs in liquids, with iodine forming ordered single-atom chains. Confined assembly also facilitated the synthesis of 1D crystals with a finite unit-cell thickness and metastable structures. We developed a SWCNT-enabled two-solvent-phase extraction strategy to synthesize single-unit-cell perovskite chains. The resulting chains exhibited unconventional stoichiometries (e.g., [Cs4PbI5]+) due to dimensionality reduction, stabilized by charge balance with SWCNT-, thus forming strong "cation-π" interactions. These single-unit-cell perovskites within the SWCNT exhibited exceptional performance in X-ray detectors due to suppressed ion migration. SWCNT-confined ordered single-unit-chain catalysts, including single-cluster and single-atom chains, with well-defined structures showed enhanced activity in redox and coupling reactions compared to their
将块状晶体还原成单链通常会产生独特的结构和性质,例如最简单的周期性、高表面体积比和量子限制效应,但它们的合成和在工作条件下的稳定仍然具有挑战性。单壁碳纳米管(SWCNTs)具有明确的1-2 nm通道,为限制合成和研究原子尺度的分子运输提供了理想的平台。此外,导电的单原子层石墨烯能够在单层石墨烯上传输物质的特性,从而实现表面特性调制和应用。SWCNTs中的固相限制组装为高温蒸汽输送提供了一种通用的替代方案,仅适用于客体热稳定和升华的情况,尽管这种情况很少实现。揭示纳米尺度上的分子运输对于深入理解组装的驱动力至关重要,进而控制具有定制性质的亚稳晶体的受限结晶。本报告总结了我们在液相受限组装方面的最新进展:(1)组装方法和机理见解;(ii)一维亚稳晶体和链的可控合成;(3)单细胞链的新特性和应用。最后,总结了目前取得的成绩和未来面临的挑战。我们采用SWCNTs和原子精确簇作为模型,从实空间角度研究液相受限组装及其机理。我们开发了一种可扩展的溶液相策略,用于在SWCNTs内组装不同的簇,而不考虑其电子性质或溶解度,这是由纳米约束和静电相互作用驱动的。先进的电子显微镜结合同步加速器x射线吸收光谱显示,SWCNTs内排列紧密的有序单簇链,而不是无序的聚集体。受限于组装现象的启发,我们证明了在液体中的SWCNTs内有效捕获重元素,包括铀和碘,其中碘形成有序的单原子链。限制组装也有利于一维晶体的合成,具有有限的单位胞厚度和亚稳结构。我们开发了一种支持swcnts的双溶剂相萃取策略来合成单单元钙钛矿链。所得到的链由于维数降低而表现出非常规的化学计量(例如,[Cs4PbI5]+),通过与SWCNT-的电荷平衡来稳定,从而形成强的“阳离子-π”相互作用。由于抑制离子迁移,这些单单元钙钛矿在swcnts中表现出优异的x射线探测器性能。swcnts约束的有序单单元链催化剂,包括单簇和单原子链,具有明确的结构,在氧化还原和偶联反应中表现出比分离的催化剂更强的活性。这些相同的单单元链与SWCNTs的导电单层石墨烯保持密切接触,使纳米管表面的电荷离域,从而增加活性位点的密度并降低激活障碍。这些纳米管约束的单单元链表现出出色的结构和操作稳定性。我们对受限组装的原子尺度见解推进了具有定制功能的一维异质结构的设计,并加深了对结构-活性关系的理解。
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引用次数: 0
Proximity Effects Leveraged in Ligand-Directed Chemical Labeling of Natural Proteins under Live Conditions 活体条件下天然蛋白质配体定向化学标记的接近效应
IF 18.3 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-11-26 DOI: 10.1021/acs.accounts.5c00646
Itaru Hamachi, Tomonori Tamura, Hiroshi Nonaka
Covalent chemical labeling of proteins is central to chemical biology, offering functional modifications beyond imaging probes. While genetically engineered systems using self-labeling tags (e.g., HaloTag, SNAP-Tag) or genetic code expansion have enabled selective labeling in live cells, endogenous (naturally occurring) proteins remain difficult targets because genetic manipulation conferring selectivity cannot be conducted. To address this, ligand-directed chemistry (LDchem) was developed in which labeling reagents combine a ligand, a probe, and a cleavable electrophile. Ligand binding forms a transient complex that guides selective covalent modification, while preserving native protein function. A key feature of LDchem is the proximity effect, where reactivity is spatially restricted to residues adjacent to the ligand-binding site. Surprisingly, the proximity in LDchem often induces accelerated reactions and unexpected modifications such as ether or ester bond formation under mild physiological (aqueous) conditions. Such proximity effects include both local concentration (ligand affinity for concentrating reagents) and orientation (linker length and rigidity for impacting residue selectivity). Studies comparing electrophiles demonstrated reaction rates spanning 4 orders of magnitude, in some cases rivaling those of self-labeling enzyme tags or even fast click reactions. Notably, weaker intrinsic electrophiles can still yield efficient labeling when favorable orientation effects prolong the residential time of reactive groups near target residues. Proximity has also been exploited for protein functionalization. For example, tethering <sup>19</sup>F-NMR probes to carbonic anhydrase converted in-cell to <sup>19</sup>F-NMR biosensors that reported their ligand binding under native conditions. Similarly, attaching fluorescent dyes to receptors allowed evaluation of ligand binding kinetics by live-cell imaging. Recent advances extend LDchem into <i>in vivo</i> systems, notably, the live mouse brain. Injection of LDchem reagents into cerebrospinal fluid enabled selective receptor labeling across whole-brain scales visualized with tissue clearing technology. Furthermore, LDchem modified endogenous receptors with a photosensitizer to develop PhoxID, a photoproximity labeling method. In live brains, this enabled proteomic mapping of receptor interactomes with 1–10 min temporal resolution, unveiling developmental shifts in α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid receptor (AMPAR)-associated proximal proteins. LDchem has also been adapted for sensing the vicinity of a target receptor. For instance, AMPARs were converted into <i>in situ</i> fluorescent biosensors to detect matrix metalloproteinase MMP-9 activity in the receptor proximity within ∼10 nm, revealing region-specific and synapse-localized enzymatic activity in the brain. In conclusion, LDchem highlights how proximity effects can be harnessed to achieve selective, accelerated, and func
蛋白质的共价化学标记是化学生物学的核心,提供超越成像探针的功能修饰。虽然使用自标记标签(例如HaloTag, SNAP-Tag)或遗传密码扩展的基因工程系统已经能够在活细胞中进行选择性标记,但内源性(天然存在的)蛋白质仍然是困难的靶标,因为无法进行赋予选择性的遗传操作。为了解决这个问题,配体定向化学(LDchem)被开发出来,其中标记试剂结合了配体,探针和可切割的亲电试剂。配体结合形成一种瞬时复合物,指导选择性共价修饰,同时保留天然蛋白质的功能。LDchem的一个关键特征是邻近效应,其中反应性在空间上仅限于与配体结合位点相邻的残基。令人惊讶的是,LDchem中的接近性通常会引起加速反应和意想不到的修饰,例如在温和的生理(水)条件下形成醚或酯键。这种接近效应包括局部浓度(用于浓缩试剂的配体亲和力)和取向(影响残留物选择性的连接体长度和刚性)。比较亲电试剂的研究表明,反应速率跨越4个数量级,在某些情况下与自标记酶标签甚至快速点击反应相媲美。值得注意的是,当有利的取向效应延长了活性基团在目标残基附近的停留时间时,较弱的本征亲电试剂仍然可以产生有效的标记。邻近性也被用于蛋白质功能化。例如,将19F-NMR探针系在碳酸酐酶上,可以将细胞内的19F-NMR生物传感器转化为在天然条件下报告其配体结合的生物传感器。同样,将荧光染料附着到受体上,可以通过活细胞成像来评估配体结合动力学。最近的进展将LDchem扩展到体内系统,特别是小鼠的活脑。将LDchem试剂注射到脑脊液中,可以通过组织清除技术在全脑范围内进行选择性受体标记。此外,LDchem用光敏剂修饰内源性受体,开发了PhoxID,一种光邻近标记方法。在活体大脑中,这使得受体相互作用组的蛋白质组学图谱具有1-10分钟的时间分辨率,揭示了α-氨基-3-羟基-5-甲基-4-异氧唑丙酸受体(AMPAR)相关近端蛋白的发育变化。LDchem也被用于感知目标受体的附近。例如,ampar被转化为原位荧光生物传感器,以检测受体附近约10 nm内基质金属蛋白酶MMP-9的活性,揭示大脑中区域特异性和突触局部化的酶活性。总之,LDchem强调了如何利用邻近效应来实现天然生物条件下的选择性、加速和功能性蛋白质标记。尽管由于靶蛋白的复杂局部环境,精确预测接近效应仍然具有挑战性,但人工智能引导的计算建模的进步有望合理设计标记试剂。这样的化学工具有望改变体内的化学生物学,使蛋白质微环境和整个生命系统中的网络的精确询问成为可能。
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引用次数: 0
Inherently Chiral Macrocycles: Catalytic Asymmetric Synthesis and Properties 固有手性大环:催化不对称合成及其性质
IF 18.3 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-11-25 DOI: 10.1021/acs.accounts.5c00609
Shuo Tong
Molecular chirality defines the non-superimposability of three-dimensional molecules onto their mirror images. Due to the often drastically distinct biological effects exhibited by enantiomers, the synthesis of enantiopure small organic molecules remains a topic of persistent research interest. Molecular chirality is commonly divided into point, axial, planar, and helical types based on stereogenic elements. In contrast, inherently chiral molecules form a unique category that lacks these conventional chiral elements. Their chirality results from curvature introduced into a planar structure without a perpendicular symmetry plane in two dimensions. A prominent example of this category is inherently chiral macrocycles (ICMs), which possess chirality solely due to their macrocyclic, nonplanar structure. Conversely, ring-opening of an ICM yields an achiral linear molecule. It is noteworthy that while the synthesis and application of conventional chiral molecules have reached a high degree of sophistication, the chemistry of ICMs remains largely unexplored, primarily due to the significant challenges in obtaining them in highly enantioenriched forms. Resolution of racemic samples using analytical HPLC with columns coated with a chiral stationary phase is the most frequently used method to obtain small amounts of enantiomers.
分子手性定义了三维分子与其镜像的不重叠性。由于对映体通常表现出截然不同的生物效应,对映不纯有机小分子的合成仍然是一个持续研究的话题。分子手性通常根据立体元素分为点型、轴型、平面型和螺旋型。相反,固有手性分子形成了一个独特的类别,缺乏这些传统的手性元素。它们的手性是由于在二维空间中没有垂直对称平面的平面结构中引入了曲率。这一类的一个突出例子是固有手性大环(ICMs),其具有手性完全是由于它们的大环,非平面结构。相反,ICM的开环产生非手性线性分子。值得注意的是,虽然传统手性分子的合成和应用已经达到了高度的复杂性,但ICMs的化学性质在很大程度上仍未被探索,这主要是因为要以高度富集对映体的形式获得它们存在重大挑战。用包覆手性固定相柱的分析高效液相色谱法分离外消旋样品是获得少量对映体最常用的方法。
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引用次数: 0
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