ACS Central Science最新文献_第3页

Spectroscopic Signatures of Phonon Character in Molecular Electron Spin Relaxation. 分子电子自旋弛豫中声子特征的光谱特征。

IF 12.7 1区化学

ACS Central Science Pub Date : 2024-12-11 eCollection Date: 2024-12-25 DOI: 10.1021/acscentsci.4c01177

Nathanael P Kazmierczak, Paul H Oyala, Ryan G Hadt

{"title":"Spectroscopic Signatures of Phonon Character in Molecular Electron Spin Relaxation.","authors":"Nathanael P Kazmierczak, Paul H Oyala, Ryan G Hadt","doi":"10.1021/acscentsci.4c01177","DOIUrl":"10.1021/acscentsci.4c01177","url":null,"abstract":"Spin-lattice relaxation constitutes a key challenge for the development of quantum technologies, as it destroys superpositions in molecular quantum bits (qubits) and magnetic memory in single molecule magnets (SMMs). Gaining mechanistic insight into the spin relaxation process has proven challenging owing to a lack of spectroscopic observables and contradictions among theoretical models. Here, we use pulse electron paramagnetic resonance (EPR) to profile changes in spin relaxation rates (T 1) as a function of both temperature and magnetic field orientation, forming a two-dimensional data matrix. For randomly oriented powder samples, spin relaxation anisotropy changes dramatically with temperature, delineating multiple regimes of relaxation processes for each Cu(II) molecule studied. We show that traditional T 1 fitting approaches cannot reliably extract this information. Single-crystal T 1 anisotropy experiments reveal a surprising change in spin relaxation symmetry between these two regimes. We interpret this switch through the concept of a spin relaxation tensor, enabling discrimination between delocalized lattice phonons and localized molecular vibrations in the two relaxation regimes. Variable-temperature T 1 anisotropy thus provides a unique spectroscopic method to interrogate the character of nuclear motions causing spin relaxation and the loss of quantum information.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"10 12","pages":"2353-2362"},"PeriodicalIF":12.7,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11672536/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142902411","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Stationary DNA Origami Register Drives Fast Sequential DNA Computing. 静止DNA折纸寄存器驱动快速序列DNA计算。

IF 12.7 1区化学

ACS Central Science Pub Date : 2024-12-11 eCollection Date: 2024-12-25 DOI: 10.1021/acscentsci.4c02006

Pu Deng, Jiahao Lin, Wei Sun

引用次数: 0

A Conversation with Olga Dudchenko. 与Olga Dudchenko的对话。

IF 12.7 1区化学

ACS Central Science Pub Date : 2024-12-11 eCollection Date: 2024-12-25 DOI: 10.1021/acscentsci.4c02010

Carolyn Wilke

引用次数: 0

The Utility of Cyclodextrin for Countering μ-Opioid Receptor Drug Overdoses. 环糊精在抗μ-阿片受体药物过量中的应用。

IF 12.7 1区化学

ACS Central Science Pub Date : 2024-12-10 eCollection Date: 2024-12-25 DOI: 10.1021/acscentsci.4c01990

Noriko Ogawa

引用次数: 0

Cyclic Ruthenium-Peptide Prodrugs Penetrate the Blood-Brain Barrier and Attack Glioblastoma upon Light Activation in Orthotopic Zebrafish Tumor Models. 环钌肽原药可穿透血脑屏障，并在直位斑马鱼肿瘤模型中通过光激活攻击胶质母细胞瘤。

IF 12.7 1区化学

ACS Central Science Pub Date : 2024-12-09 eCollection Date: 2024-12-25 DOI: 10.1021/acscentsci.4c01173

Liyan Zhang, Gangyin Zhao, Trevor Dalrymple, Yurii Husiev, Hildert Bronkhorst, Gabriel Forn-Cuní, Bruno Lopes-Bastos, Ewa Snaar-Jagalska, Sylvestre Bonnet

{"title":"Cyclic Ruthenium-Peptide Prodrugs Penetrate the Blood-Brain Barrier and Attack Glioblastoma upon Light Activation in Orthotopic Zebrafish Tumor Models.","authors":"Liyan Zhang, Gangyin Zhao, Trevor Dalrymple, Yurii Husiev, Hildert Bronkhorst, Gabriel Forn-Cuní, Bruno Lopes-Bastos, Ewa Snaar-Jagalska, Sylvestre Bonnet","doi":"10.1021/acscentsci.4c01173","DOIUrl":"10.1021/acscentsci.4c01173","url":null,"abstract":"The blood-brain barrier (BBB) presents one of the main obstacles to delivering anticancer drugs in glioblastoma. Herein, we investigated the potential of a series of cyclic ruthenium-peptide conjugates as photoactivated therapy candidates for the treatment of this aggressive tumor. The three compounds studied, Ru-p(HH), Ru-p(MH), and Ru-p(MM) ([Ru(Ph2phen)2 (Ac-X1RGDX2-NH2)]Cl2 with Ph2phen = 4,7-diphenyl-1,10-phenanthroline and X1, X2 = His or Met), include an integrin-targeted pentapeptide coordinated to a ruthenium warhead via two photoactivated ruthenium-X1,2 bonds. Their photochemistry, activation mechanism, tumor targeting, and antitumor activity were meticulously addressed. A combined in vitro and in vivo study revealed that the photoactivated cell-killing mechanism and their O2 dependence were strongly influenced by the nature of X1 and X2. Ru-p(MM) was shown to be a photoactivated chemotherapy (PACT) drug, while Ru-p(HH) behaved as a photodynamic therapy (PDT) drug. All conjugates, however, showed comparable antitumor targeting and efficacy toward human glioblastoma 3D spheroids and orthotopic glioblastoma tumor models in zebrafish embryos. Most importantly, in this model, all three compounds could effectively cross the BBB, resulting in excellent targeting of the tumors in the brain.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"10 12","pages":"2294-2311"},"PeriodicalIF":12.7,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11672551/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142902390","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

From Beam Damage to Massive Reaction Amplification under the Electron Microscope: An Ionization-Induced Chain Reaction in Crystals of a Dewar Benzene. 从电子束损伤到电子显微镜下的大规模反应放大：杜瓦苯晶体中电离诱导的链式反应。

IF 12.7 1区化学

ACS Central Science Pub Date : 2024-12-06 eCollection Date: 2024-12-25 DOI: 10.1021/acscentsci.4c01429

Krzysztof A Konieczny, Indrajit Paul, Jose A Rodriguez, Miguel A Garcia-Garibay

引用次数: 0

Targeted Radionuclide Therapy Activates Prodrugs for Treating Metastasis. 靶向放射性核素疗法激活治疗转移的前药。

IF 12.7 1区化学

ACS Central Science Pub Date : 2024-12-05 eCollection Date: 2024-12-25 DOI: 10.1021/acscentsci.4c01369

Zhibin Guo, Xuanyu Wang, Yi Han, Siyong Shen, Peng Tian, Yuchen Hu, Zexuan Ding, Qunfeng Fu, Zhibo Liu

{"title":"Targeted Radionuclide Therapy Activates Prodrugs for Treating Metastasis.","authors":"Zhibin Guo, Xuanyu Wang, Yi Han, Siyong Shen, Peng Tian, Yuchen Hu, Zexuan Ding, Qunfeng Fu, Zhibo Liu","doi":"10.1021/acscentsci.4c01369","DOIUrl":"10.1021/acscentsci.4c01369","url":null,"abstract":"Over 90% of cancer patients succumb to metastasis, yet conventional frontline therapy struggles to halt the progression of metastatic tumors. Targeted radionuclide therapy, which delivers radiation precisely to tumor sites, shows promise for treating metastasis. The rational design of a prodrug activation platform using radionuclides would be an ideal approach to synergize chemotherapy with targeted radionuclide therapy, yet it has not been established. Here, we present targeted radionuclide therapy-induced cleavage chemistry that enables the controlled release of oxaliplatin and its axis ligands from oxaliplatin(IV) complexes in living systems. Of note, this strategy demonstrates feasibility over clinically relevant β-emitting radionuclides and exhibits dose dependence. These advantages were taken into account, and a Lutetium-177-activatable platinum(IV) based prodrug system was designed that could achieve localized activation at the tumor site with high efficiency, thereby suppressing subcutaneous and metastatic 4T1 tumors. In summary, our approach highlights the potential of radionuclides as reaction switches, bridging the gap between the radiotherapy-induced reaction and internal radiation. It may provide a new perspective for future combination therapy.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"10 12","pages":"2321-2330"},"PeriodicalIF":12.7,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11672548/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142902416","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Reconfigurable Amphiphilic DNA Nanotweezer for Targeted Delivery of Therapeutic Oligonucleotides. 用于靶向递送治疗性寡核苷酸的可重构两亲性DNA纳米镊子。

IF 12.7 1区化学

ACS Central Science Pub Date : 2024-12-05 eCollection Date: 2024-12-25 DOI: 10.1021/acscentsci.4c01152

Shuxuan Shao, Wei Du, Shuang Liu, Canqiong Hu, Cao Zhang, Lexun Li, Fan Yang, Qiaoling Liu, Weihong Tan

{"title":"Reconfigurable Amphiphilic DNA Nanotweezer for Targeted Delivery of Therapeutic Oligonucleotides.","authors":"Shuxuan Shao, Wei Du, Shuang Liu, Canqiong Hu, Cao Zhang, Lexun Li, Fan Yang, Qiaoling Liu, Weihong Tan","doi":"10.1021/acscentsci.4c01152","DOIUrl":"10.1021/acscentsci.4c01152","url":null,"abstract":"Amphiphilic lipid oligonucleotide conjugates are powerful molecular-engineering materials that have been used for delivery of therapeutic oligonucleotides. However, conventional lipid oligonucleotide conjugates suffer from poor selectivity to target cells due to the nonspecific interaction between lipid tails and cell membranes. Herein, a reconfigurable DNA nanotweezer consisting of a c-Met aptamer and bischolesterol-modified antisense oligonucleotide was designed for c-Met-targeted delivery of therapeutic antisense oligonucleotides. The c-Met aptamer is used to keep the DNA nanotweezer in a \"closed\" state, which enables the hydrophobic interaction within bischolesterol moieties. As a result, the amphiphilic DNA nanotweezer shows only a weak interaction with the cell membrane. Upon the release of the c-Met aptamer, the DNA nanotweezer converts to an \"open\" state, which facilitates the insertion of a cholesterol moiety into the cell membrane. Thus, the reconfigurable DNA nanotweezer enables the selective membrane anchoring of the DNA nanotweezer in cancerous cells that highly expressed c-Met protein. Moreover, this amphiphilic DNA nanotweezer shows enhanced accumulation at the tumor site and the inhibition of tumor growth. Taking advantage of the stimuli-responsive membrane anchoring capability, this reconfigurable DNA nanotweezer could be further explored as a smart multifunctional platform for cancer therapy.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"10 12","pages":"2338-2345"},"PeriodicalIF":12.7,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11672532/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142902408","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Proton-Transfer Dynamics Regulates CO₂ Electroreduction Products via Hydrogen Coverage. 质子转移动力学通过氢覆盖调节CO2电还原产物。

IF 12.7 1区化学

ACS Central Science Pub Date : 2024-11-28 eCollection Date: 2024-12-25 DOI: 10.1021/acscentsci.4c01534

Qun Fan, Tiantian Xiao, Hai Liu, Tianxiang Yan, Jianlong Lin, Siyu Kuang, Haoyuan Chi, Thomas J Meyer, Sheng Zhang, Xinbin Ma

{"title":"Proton-Transfer Dynamics Regulates CO2 Electroreduction Products via Hydrogen Coverage.","authors":"Qun Fan, Tiantian Xiao, Hai Liu, Tianxiang Yan, Jianlong Lin, Siyu Kuang, Haoyuan Chi, Thomas J Meyer, Sheng Zhang, Xinbin Ma","doi":"10.1021/acscentsci.4c01534","DOIUrl":"10.1021/acscentsci.4c01534","url":null,"abstract":"Electrochemical conversion of CO2 to hydrocarbons is a promising approach to carbon neutrality and energy storage. The formation of reaction intermediates involves crucial steps of proton transfer, making it essential to understand the role of protons in the electrochemical process to control the product selectivity and elucidate the underlying catalytic reaction mechanism of the CO2 electrochemical reduction (CO2RR). In this work, we proposed a strategy to regulate product selectivities by tuning local proton transport rates through a surface resin layer over cuprous oxides. We systematically studied the influence of proton transfer rates on product selectivities by regulating the polymerization degree of resorcinol-formaldehyde resin (RF). The production of C2 compounds and CH4 could be switched through an RF coating with the maximum CH4 Faradaic efficiency of 51% achieved at current densities close to the amperage level. Both experimental and theoretical calculation results suggest that the resin layer can subtly alter proton transfer rates during the electrochemical process, thereby influencing the hydrogen coverage on catalytic sites and ultimately guiding the overall electrochemical performance toward product selectivity.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"10 12","pages":"2331-2337"},"PeriodicalIF":12.7,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11672531/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142902407","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The New Paradigm of Ligand Substitution-Driven Enhancement of Anisotropy from SO₄ Units in Short-Wavelength Region. 配体取代驱动SO4单元在短波长区域增强各向异性的新范式。

IF 12.7 1区化学

ACS Central Science Pub Date : 2024-11-27 eCollection Date: 2024-12-25 DOI: 10.1021/acscentsci.4c01401

Chenhui Hu, Huimin Li, Guangsheng Xu, Zhihua Yang, Jian Han, Shilie Pan

{"title":"The New Paradigm of Ligand Substitution-Driven Enhancement of Anisotropy from SO4 Units in Short-Wavelength Region.","authors":"Chenhui Hu, Huimin Li, Guangsheng Xu, Zhihua Yang, Jian Han, Shilie Pan","doi":"10.1021/acscentsci.4c01401","DOIUrl":"10.1021/acscentsci.4c01401","url":null,"abstract":"For non-π-conjugated [SO4] units, it is challenging to generate sufficient birefringence, owing to the high symmetry of the regular tetrahedron. Unlike the traditional trial-and-error approach, we propose a new paradigm for birefringence engineering to tune the optical properties based on [SO4] units. Through the strategy of ligand substitution, we can predict its effect on the band gap and anisotropy. Theoretical evaluations reveal generalized results that the anisotropic electron distribution of new functional groups induced by the suitable ligand substitution contributes to the band gap and birefringence. To further validate the correctness of the paradigm, we experimentally synthesized and characterized nine novel compounds with selected functional modules. By the new paradigm of ligand substitution, they can reach up to 4-6 times the birefringence of the corresponding sulfate and maintain the wide bandgap. Through rational design, (CN4H7)SO3NH2 exhibits about 35 times the birefringence of Li2SO4, which is a significant order of magnitude improvement and verifies the superiority of our proposed paradigm. This work provides a new paradigm for the modification to the non-π-conjugated group and will guide and accelerate the exploration of novel birefringent crystals in the short-wavelength region.","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"10 12","pages":"2312-2320"},"PeriodicalIF":12.7,"publicationDate":"2024-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11673188/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142902419","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0