Article
Multidisciplinary Sciences
Nasim Sadat Mosavi, Eugenia Ribeiro, Adriana Sampaio, Manuel Filipe Santos
Summary: This exploratory study used data mining techniques to investigate the role of different therapist and client factors, including heart rate and electrodermal activity, in relation to Therapeutic Alliance (TA). The results showed that client Diagnostic and therapy Termination were significant predictors of the therapist's TA, and the Random Forest technique had the best performance in predicting clients' TA. The therapist's TA and therapy Outcome were observed as the most influential predictors for the client's TA, and heart rate (therapist) and electrodermal activity (client) were found to be associated with the therapist's and client's TA, respectively.
SCIENTIFIC REPORTS
(2023)
Article
Chemistry, Multidisciplinary
Tobias Kaper, Dennis Geik, Felix Fornfeist, Marc Schmidtmann, Sven Doye
Summary: Intermolecular hydroaminoalkylation reactions of symmetrical and unsymmetrical alkynes with tertiary amines were achieved with catalytic amounts of TiBn4, Ph3C[B(C6F5)(4)], and a sterically demanding aminopyridinato ligand precursor. The resulting products, synthetically and pharmaceutically useful tertiary beta,gamma-disubstituted allylic amines, were obtained in high yields and excellent stereoselectivity. The fact that even the industrial side product trimethylamine can be used as a substrate is particularly promising for future applications.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Dennis Geik, Michael Rosien, Jens Bielefeld, Marc Schmidtmann, Sven Doye
Summary: A novel cationic titanium catalyst system was developed for intermolecular hydroaminoalkylation of alkenes with tertiary alkylamines, resulting in excellent regioselectivity towards branched products. Interestingly, alpha-C-H bond activation was observed not only at N-methyl but also at N-methylene groups for selected amines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Huaquan Fang, Kaixue Xie, Sebastian Kemper, Martin Oestreich
Summary: The study demonstrates that Tris(pentafluorophenyl)borane catalyzes the two-fold C(sp(3))-H silylation of various trialkylamine derivatives with dihydrosilanes, resulting in the formation of 4-silapiperidines in decent yields. The reaction cascade involves amine-to-enamine dehydrogenation at two alkyl residues and two electrophilic silylation reactions of those enamines, one inter- and one intramolecular.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Samantha L. Goldschmid, Nicholas Eng Soon Tay, Candice L. Joe, Brendan C. Lainhart, Trevor C. Sherwood, Eric M. Simmons, Melda Sezen-Edmonds, Tomislav Rovis
Summary: Aryl amination plays a crucial role in medicinal, process, and materials chemistry. Blue-light-driven metallaphotoredox catalysis is a valuable tool for C-N cross-coupling, but its limited penetration through reaction media and the formation of unwanted side-products pose challenges for industrial scalability. Using low-energy light, such as deep red or near-infrared, can enhance penetration and suppress unwanted reactions, leading to an enhanced scope of aryl bromides and amine-based nucleophiles.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Inorganic & Nuclear
Joao Guilherme M. de Carvalho, Korbinian Geisser, Sebastian J. Weishaeupl, Roland A. Fischer, Alexander Poethig
Summary: A tetratopic bis(diphenylamino)anthraquinone linker is presented in this study. Its physicochemical and emissive properties are evaluated, and it successfully coordinates alkaline earth metals to form four new reported metal-organic frameworks (MOFs). The catalytic behavior of the ligand and the MOF materials towards the photooxidation of sulfides is also described.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jesus Rodrigalvarez, Luke A. Reeve, Javier Miro, Matthew J. Gaunt
Summary: This article reports a simple and efficient method for introducing aryl groups into aminomethyl-cyclopropanes and -cyclobutanes through enantioselective C-H arylation, which simplifies the construction of functionalized strained aminomethyl-cycloalkanes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Organic
Oleg Afanasyev, Ekaterina A. Kuchuk, Karim M. Muratov, Gleb L. Denisov, Denis Chusov
Summary: Tertiary amines are key organic molecules with various industrial, synthetic, and analytical applications. Different methods for synthesizing C-3 and C-3V symmetrical tertiary amines include N-alkylation, reductive amination, desamination, hydroamination of olefins, and various C-N cross-coupling reactions. The advantages and disadvantages of each method for preparing the titled structures are discussed in the review.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Liwen Liu, Yu Liu, Xue Shen, Xiao Zhang, Shengqi Deng, Yang Chen
Summary: A simple, mild, catalyst-free, and efficient reductive cyanation reaction of tertiary amides mediated by (KOBu)-Bu-t under hydrosilylation conditions has been reported. A series of alpha-aminonitriles are obtained in moderate to high yields with good tolerance towards various functional groups. The reaction utilizes readily available amide substrates, a cheap and versatile base (KOBu)-Bu-t, and a commercially available hydrosilane (EtO)(3)SiH, and is convenient for workup and purification.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Popuri Sureshbabu, Sadaf Azeez, Koyal Pattanaik, Shahulhameed Sabiah, Jeyakumar Kandasamy
Summary: A wide range of aryl and alkyl N-Cbz amides were successfully prepared using LiHMDS and DBU, and their application in transamidation and transesterification reactions was demonstrated. The method exhibits a broad substrate scope and high yields.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Shweta Singh, Popuri Sureshbabu, Shahulhameed Sabiah, Jeyakumar Kandasamy
Summary: In this study, the synthesis of N-aryl alpha-ketoamides, alpha-ketoesters, and alpha-ketothioesters from N-Ts and N-Boc alpha-ketoamides via transamidation and transesterification reactions was demonstrated. The reactions were conducted at room temperature with DBU as the catalyst, resulting in the desired products in good to excellent yields and short reaction times. Furthermore, a regioselective synthesis of biologically relevant quinoxalinones was achieved from N-aryl alpha-ketoamides through nitration and reduction reactions, providing good yields.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Kaixiu Luo, Yongqiang Zhao, Zhiliang Tang, Weina Li, Jun Lin, Yi Jin
Summary: In this paper, we describe a method for the dual C(sp3)-H bond functionalization of tertiary amine through hydride-transfer-induced dehydrogenation and cycloaddition, using an easily preparable diazoester as a new type of hydride-acceptor precursor under mild, redox-neutral conditions. By using carbene as a hydrogen acceptor, a variety of functionalized isoxazoldines can be prepared in moderate to good yields.
Article
Chemistry, Multidisciplinary
Kejian Li, Kedong Gong, Juan Liu, Lukas Ohnoutek, Jianpeng Ao, Yangyang Liu, Xi Chen, Guanjun Xu, Xuejun Ruan, Hanyun Cheng, Jin Han, Guodong Sui, Minbiao Ji, Ventsislav K. Valev, Liwu Zhang
Summary: In this study, it was found that decreasing the diameter of microdroplets significantly increases the reaction rate of dye oxidation using Fe(III)-oxalate photochemistry and g-C3N4 photocatalysis. This rate increase is attributed to the change in interface properties of microdroplets. The results of this study have important implications for improving the efficiencies of photochemistry and photocatalysis, as well as atmospheric photochemistry.
CELL REPORTS PHYSICAL SCIENCE
(2022)
Article
Chemistry, Physical
Ivan S. Zhidkov, Danil W. Boukhvalov, Azat F. Akbulatov, Lyubov A. Frolova, Larisa D. Finkelstein, Andrey Kukharenko, Seif O. Cholakh, Chu-Chen Chueh, Pavel A. Troshin, Ernst Z. Kurmaev
Summary: This article explores the degradation processes in APbX(3) hybrid halide perovskites using XPS and DFT, finding a correlation between stability and the formation of PbX2 degradation product, which can be monitored and confirmed by high-energy XPS and DFT calculations. Moreover, it shows an increasing resistance to stress factors with the substitution of A-site cation from CH3NH3+ to CH(NH2)(2)(+) and then to Cs+.
Article
Biophysics
Anna H. Lippert, Ivan B. Dimov, Alexander K. Winkel, Jane Humphrey, James McColl, Kevin Y. Chen, Ana M. Santos, Edward Jenkins, Kristian Franze, Simon J. Davis, David Klenerman
Summary: Research suggests that the early stages of T cell activation may not be influenced by substrate rigidity, while later stages may be associated with substrate stiffness.
Exclusion of large receptor-type phosphatases was observed on soft bilayers.
This work lays the groundwork for exploring receptor signaling under physiological cell-cell contact conditions.
BIOPHYSICAL JOURNAL
(2021)
Article
Chemistry, Physical
Naeem Asad, Davide Deodato, Sangram Gore, Timothy M. Dore
Summary: By functionalizing four derivatives, the release of tertiary amines via two-photon excitation (2PE) was studied. These derivatives exhibited good properties in biological settings and an optimized photoremovable protecting group (PPG) mediated the efficient photoactivation of various biological effectors.
Article
Chemistry, Multidisciplinary
Ziqi Deng, Lan Li, Han Jia, Nga-Fong Li, Jiaxing He, Ming-De Li, David Lee Phillips, Ying Li
Summary: The photodynamics of different halogen-substituted MG derivatives and their corresponding FAP-MG complexes were studied using femtosecond transient absorption spectroscopy and theoretical computations. The results showed that FAP binding restricts the rotation of MG, leading to longer excited state lifetimes and enhanced fluorescence emission and singlet oxygen generation. This study will contribute to the development of advanced FAP-MG systems with high spatiotemporal resolution.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Microbiology
Rajani Ravishankar, Emily R. Hildebrandt, Grace Greenway, Nadeem Asad, Sangram Gore, Timothy M. Dore, Walter K. Schmidt
Summary: CAAX proteins undergo various posttranslational modifications, and this study used a proteolysis-resistant CAAX sequence to investigate Saccharomyces cerevisiae Ras2 GTPase. The results showed that the type of CAAX motif affected Ras2 protein levels, localization, and function.
MICROBIOLOGY SPECTRUM
(2023)
Article
Chemistry, Physical
Yuanchun Li, Qidi Zhang, Kin Cheung Lo, Zhiping Yan, David Lee Phillips, Wenjian Tang, Lili Du
Summary: Photoremovable protecting groups have significant importance in controlling the release of various reactive species in a temporally and spatially controlled manner. This study provides an in-depth investigation into the heterolysis-solvolysis reaction mechanisms of a specific photoremovable protecting group, 3',5'-dimethoxybenzoin (DMB) chloride. Experimental techniques, such as transient absorption and time-resolved resonance Raman spectroscopies, were used to directly observe the features of the intermediates formed during the photolysis process. The study also revealed the presence of a long-lived alpha-keto cation intermediate as a key intermediate in the reaction mechanism of DMB chloride.
JOURNAL OF PHYSICAL CHEMISTRY B
(2023)
Article
Chemistry, Physical
Qian-qian Tan, Yan Guo, David Lee Phillips, Tongyu Xu, Jiani Ma
Summary: Femtosecond transient absorption, nanosecond transient absorption, and nanosecond resonance Raman spectroscopy techniques combined with density functional theory calculations were used to investigate the photocyclization and photorelease mechanisms of a diarylethene compound. This study provides a deeper understanding of these reactions and can aid in the future design of functionalized diarylethene derivatives for specific applications.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Biochemistry & Molecular Biology
Ka Wa Fan, Hoi Ling Luk, David Lee Phillips
Summary: The 3-hydroxyflavone (3-HF) is a common fluorescence probe with two distinct fluorescence bands. However, it has poor performance in water due to hydrogen bonding perturbation. The use of supramolecular chemistry improves its fluorescence performance in water. This paper reviews the supramolecular chemistry of 3-hydroxyflavone with cyclodextrin and octa acid, showing that beta-cyclodextrin slightly improves the fluorescence intensity of the tautomer form, gamma-cyclodextrin enhances the green fluorescence intensity, and octa acid creates a dry environment for 3-hydroxyflavone to exist only in the tautomer form.
Article
Chemistry, Organic
T. E. Anderson, Dasan M. Thamattoor, David Lee Phillips
Summary: The rearrangement pathways of two alkylidene carbenes appended to an oxa or thiacyclopentane into the corresponding heterocyclohexynes were investigated through 13C-labeling experiments. Both carbenes showed a preferential migration of the allylic carbon bound to the heteroatom. Anomeric interactions involving a heteroatom lone pair and the antibonding orbital of the migrating bond, as well as the inductive destabilization of the minor migratory pathway, were proposed as plausible reasons for the observed trends.
Article
Chemistry, Physical
Shihuai Wang, Xutao Gao, Xiaoyong Mo, David Lee Phillips, Edmund C. M. Tse
Summary: positioning basic/acidic groups near a molecular catalyst can modulate proton-coupled electron transfer reactions in energy conversion and storage. In this study, a copper(II) dipicolylamine catalyst was immobilized on a metal oxide electrode to investigate the activity of oxygen reduction reaction (ORR) in aqueous solution. The addition of a carboxylateterminated ligand onto the metal oxide surfaces significantly enhanced the catalytic current of ORR by three times. The enhanced activity was attributed to a hydrogen bond formed between the proximal carboxylate of the cocatalyst and a Cu-OOH intermediate.
Article
Chemistry, Physical
Zi-Gang Lu, Wenbin Chen, David Lee Phillips, Ming-De Li
Summary: In this study, blebbistatin derivatives with various electronic characteristic leaving groups were synthesized and studied to unveil the photocleavage mechanism(s) and the tunable effect of the leaving groups. The results provide a structure-property relationship that allows for rational selection of protected groups in molecules for specific applications.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Shihuai Wang, Xutao Gao, Xiaoyong Mo, David Lee Phillips, Edmund C. M. Tse
Summary: Positioning basic/acidic groups near a molecular catalyst is a popular strategy to modulate proton-coupled electron transfer reactions. The real role played by these groups, however, remains unclear. In this study, the CuL catalyst was immobilized on a metal oxide electrode to investigate its activity in the oxygen reduction reaction. The catalytic current of the CuL catalyst was enhanced by three times when a carboxylate-terminated ligand was integrated onto the metal oxide surface as a cocatalyst. The CuL-coated metal oxide electrode with a carboxylate-terminated cocatalyst exhibited higher turnover frequency values compared to other cases.
Article
Biochemistry & Molecular Biology
Naeem Asad, Davide Deodato, Nadeem Asad, Sangram Gore, Timothy M. Dore
Summary: Phenols confer bioactivity to a plethora of organic compounds. Protecting the phenolic functionality with photoremovable protecting groups (PPGs) sensitive to two-photon excitation (2PE) can block the bioactivity and provide controlled release of these compounds. A study found that a two-photon sensitive PPG can efficiently release phenols and has attributes useful for biological use. The findings are important for understanding neurological signaling and the roles of neurotransmitters.
ACS CHEMICAL NEUROSCIENCE
(2023)
