Zhu Jin
Ph.D. Advisor
Phone Number: 13851539572
Office Address: C415
E-mail: jinz@nju.edu.cn
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Personal Profile

Born 1971. Prof. Jin Zhu holds a B.S. degree from Nanjing University (1992), a M.S. degree from the Institute of Chemistry, Chinese Academy of Sciences (1995), and a Ph.D. degree from Northwestern University, USA (1999). He was conducting research at the University of California at Santa Barbara, USA and Japan Science and Technology Agency, Japan prior to becoming a professor at NanjingUniversity in 2005.


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Research

Observations and hypotheses are the two fundamental pillars of modern science. Our research is focused on broadening the spectrum of observations and hypotheses (beyond the current norm and broadly defined). This translates to the expansion of the structural, functional, and mechanistic scope of synthesis.

The first observations made in polymer and materials synthesis include low-temperature depolymerization of vinyl polymer (follow-up observations by: David M. Haddleton, University of Warwick; Krzysztof Matyjaszewski, Carnegie Mellon University; Mitsuo Sawamoto, Kyoto University; Brent S. Sumerlin, University of Florida; Athina Anastasaki, ETH Zurich), highly deliquescent property of polymer (follow-up observation by: Shigetaka Hayano, Zeon Corporation), solvent-driven organogel shrinkage (follow-up observation by: Masahiko Yamaguchi, Tohoku University), and self-assembly fractionation of polymer. Molecular plastics programming is proposed as an effective platform for mapping of polymer chain architecture to physical properties. Molecular plastics programming refers to a molecular-macroscopic-correspondence-prescribing strategy viewing a monomer unit as a divisible entity comprised of a set of building blocks, with each building block contributing to the acquirement of target plastic properties, ideally in an accurately predictable manner, when integrated into a polymer chain architecture.

In biological and organic synthesis, formalization of observations and formulation of hypotheses have been practiced. Chemical catalysis is characterized by the operation of an open-boundary catalytic center, without a partially or fully folded catalytic cavity. Enzymatic catalysis is distinguished by the engagement of a closed-boundary catalytic center, with a partially or fully folded catalytic cavity. Reciprocal conformational adaptation refers to a phenomenon that both enzyme and substrate can undergo substantial conformational changes for reciprocal adaptation to each other’s conformational constraints during an enzymatic binding and catalysis event. The combination of a closed-boundary catalytic architecture and reciprocal conformational adaptation presents a generic pathway to simultaneously, a broad substrate scope and quantitative enantioselectivity. Stringency-relaxation refers to an enzymatic catalysis strategy that operates through the initial stringency creation of catalysis-requisite amino acid set for exclusive catalytic access to the catalytically most demanding functional group (requiring the largest number and most synergistic collaboration of critical amino acids), followed by subsequent relaxation of amino acid set (mutational change of part of the amino acid set for the catalytically most demanding functional group and attenuation of the amino acid catalytic and/or anchoring effect; termed as amino acid relaxation herein) for exclusive catalytic access to the catalytically less demanding functional group. Reactivity chemistry refers to a static descriptor system for an organic transformation that exclusively asserts functional group already in existence as the root for originating the reactive site of interest. Reactivity transduction chemistry refers to a dynamic reactive unit descriptor system that refers to the delineation of emergence of reactivity (or reactivity flow) based on reactive fragment mapping, the flow of predecessor reactive fragments into the descendant reactive fragment of interest. Reactivity-depleting synthesis refers to the creation, selection, and exploitation of reactivity associated with reactive entities (e.g., heteroatom sites, functional groups) on the reactant side for the projected bonding transformation, and in the service of establishing a target core structure on the product side, thus frequently witnessing the annihilation of product inner reactivity. Reactivity-propagating synthesis refers to the simultaneous accommodation of both reactant reactivity and product inner reactivity into synthetic design, with the survival of product inner reactivity as a central goal. Reactivity speciation refers to a synthetic practice perceiving a priori the reactants as, out of a set of reactive units, a static supply pool of reactive units with definitive complementary matching of reactivity (definitive reactive unit partners) for the deterministic pathway to a specific product. Reactivity adaptation speciation refers to a synthetic practice perceiving the reactants as a dynamic supply pool of shifting reactive units emanated from and compliant with the opportunistic complementary matching of reactivity (shifting reactive unit partners) for the diverse-manifold commensurate pathways to varied products. Site-centered reactivity refers to a synthetic practice for the discovery of organic transformations, with discrete functional group sites as the center of focus for eliciting reactivity and conversions. Skeleton-chaperoned reactivity refers to a synthetic practice with skeleton as a structural scaffold for assisting the activation of functional group sites into a proper reactive sequence. Joint radical effect refers to a phenomenon that the polarity of a radical can be influenced by a covalently bonded, jointed structure as perceived along the reaction trajectory. Disjoint radical effect refers to a phenomenon that the polarity of a radical can be influenced by a non-covalently associated, disjointed structure. Dynamic radical effect refers to a phenomenon that the bonding association between two radicals is reversible and upon bonding dissociation, one radical proceeds to the target reaction course without the participation of other radical. Skeleton speciation-oriented synthesis refers to a synthetic modality that prioritizes synthetic organic speciation by the key bond transformation event and the correspondingly forged primary skeleton, with the associated peripheral appendages viewed as a secondary accessory. Appendage speciation-oriented synthesis refers to a synthetic modality that prioritizes synthetic organic speciation primarily by the peripheral appendages in line with the key bond transformation event and subsequent peripheral bond manipulation, with the skeleton viewed as a secondary accessory. Dynamic polarity analysis refers to the electronic character assignment of both static polarity and transient polarity (transient species-generated polarity, other than static polarity) at each site as well as associated complementarity, for reacting partners. A chemistry set refers to a collection of transformations with defined (especially quantitative) reactivity relations. Set chemistry refers to a synthetic programming strategy, with chemistry set, rather than individual transformation, as the fundamental unit for synthetic planning. Neighboring appendage participation conceptualizes the neighboring appendage-participated inclusive conversion of an otherwise anionically charged, poor leaving group into a neutral, good leaving group (e.g., assisted protonation through the interaction of nonbonding valence electrons with π electrons), for the promotion of bond cleavage. Organic metathesis reactions, typically involving the participation of at least two-carbon- or one-carbon-plus-one-hydrogen-derived covalent bonds, can be divided into three broad categories based on the use of two descriptors: elemental connectivity and bonding modes. The metathesis with an identical set of both elemental connectivity and bonding modes before and after the molecular fragment exchange process is termed as homomorphic metathesis (e.g., olefin-olefin metathesis, olefin-carbonyl metathesis) and as heteromorphic metathesis otherwise. The metathesis with a different set of elemental connectivity (and naturally, a different set of bonding modes) upon molecular fragment exchange is termed as connectivity-heteromorphic metathesis (e.g., Wittig reaction). The metathesis with an identical set of elemental connectivity but a different set of bonding modes upon molecular fragment exchange is termed as bonding-heteromorphic metathesis (e.g., catalytic olefin-imine metathesis reported by our group). Homeostatic catalysis refers to a catalytic process that can sustain its productive catalytic cycle even when chemically disturbed. A relay formalism is introduced to categorize the transition metal catalysis mechanisms; transition metal catalysis can be perceived as a continuous relay of the catalytic center from product (donor) to one reactant (acceptor) and can proceed by either dissociative relay or associative relay mode; the dissociative relay refers to a process of passing an innocent catalytic center, in an intermediate product-released and reactant-free state, to one reactant (acceptor), whereas the associative relay involves the passing of a non-innocent catalytic center through the competitive release of product by one additional reactant (acceptor). A reactivity relay cascade formalism is proposed to delineate the reactivity site transfer process; a reaction can encompass either one reactivity paradigm, identified as a reactivity site relay trajectory featuring reactivity initiation to termination by a discrete closed suite of electron pushing pathways (from the perspective of electron pushing formalism, each prior electron pushing pathway acting as a necessary condition for the ensuing electron pushing pathway), or multiple reactivity paradigms accommodated into a consecutive reactivity paradigm relay trajectory (from the perspective of electron pushing formalism, each prior reactivity paradigm acting as neither a necessary nor a sufficient condition for the ensuing reactivity paradigm). A polarity relay concept is used to generalize the observations of polarity matching-mediated ring-closure transformations. A skeleton-oriented synthesis concept is devised as a complementary thought framework for efficient synthesis as opposed to target-oriented synthesis and diversity-oriented synthesis; skeleton-oriented synthesis refers to a traceless appendage planning synthetic strategy for constructing molecular skeletons, with unintended appendages from the reactivity-assisting groups eliminated, and utility of the accessible reactivity of ring atoms for attaching intended appendages. Forward reactivity analysis is emphasized as a useful tool for streamlining the synthesis by the forward synthetic planning of synergism in reactivity of coupling partners in a consecutive reaction. A first catalytic olefin-imine metathesis has been achieved, providing a mechanistic basis for the innovative manipulation of C=C/C=N bond exchange process. A first synthesis of cobaltacycle intermediate has been achieved under catalysis-relevant C-H bond activation condition, providing direct experimental evidence for the first-row transition metal-catalyzed C-H bond activation reactions. Following our proposed C-H activation methods, other groups have developed a plethora of synthetic reactions: N-nitroso (44 follow-up reactions), enaminone (15 follow-up reactions), N-chloroamide (7 follow-up reactions), N-amino (5 follow-up reactions), oxadiazole (2 follow-up reactions), 2-hydrazinylpyridine (1 follow-up reaction). In addition, other groups have developed 4 and 1 follow-up reactions based on our proposed dihydroquinazolinone- and benzothiazoline-mediated photolytic C-C bond cleavage methods. Over 210 review articles have introduced our synthetic approaches, with 3 exclusively highlighting N-nitroso-directed C-H bond functionalization and 1 exclusively highlighting enaminone-directed C-H bond functionalization.

In biological synthesis, a decentralized approach for the formulation of hypotheses is proposed. The centralized hypothesis formulation approach, which exploits a primary phenomenon to extract a dominant hypothesis, has monopolized scientific thinking and practice for centuries. The major flaw of this essentially ad hoc approach is that it can constrict the conceivable experimental boundaries, thwart quest for alternative legitimate hypotheses, and ultimately hinder understanding of the system of interest. In contrast, our decentralized approach operates through preconception-free phenomenon accumulation and parallel, reticular logical reasoning processes, thus offering an objective, inclusive view of the system and allowing the derivation of a set of more coherent and tenable hypotheses. Through this approach, a hierarchical model has been established for a prion self-assembled structure, enabling comprehensive insight into hitherto elusive static and dynamic aspects of this intriguing system.

A series of sequence-specific biomacromolecular characterization methods (monolayer-barcoded nanoparticle, fluorous tag, biomineralization, etc.; for circumvention of thermodynamic bottleneck, elimination of competitive interference, multiplexed parallel assay of sequences) has been proposed and demonstrated for molecular diagnostics applications (follow-up studies by: Peter Sjövall, Fredrik Höök, Chalmers University of Technology; Hubert H. Girault, Ecole Polytechnique Fedé rale de Lausanne, etc.).

Publications

Understanding/Creating Chemical/Biological Structures/Functions at the Atomic/Molecular Level: Synthetic Chemistry (Polymer, Organic, and Biological).

1. For the first observation of depolymerization of vinyl polymers (with the same type of phenomenon observed afterwards by other groups), please see: Polymer 2012, 53, 5010.

2. For my view on science (a decentralized approach to the formulation of hypotheses), please see: Scientific Reports 2016, 6, 30633. Open Access DOI: 10.1038/srep30633.

3. For the first observation of self-assembly fractionation of polymers, please see: https://doi.org/10.26434/chemrxiv-2025-f5113.

4. For the concepts of open-boundary catalytic architecture (chemical catalysis), closed-boundary catalytic architecture (enzymatic catalysis), and reciprocal conformational adaptation (enzymatic catalysis), please see: https://doi.org/10.26434/chemrxiv-2025-6zgnq-v2.

5. For the concept of enzymatic stringency-relaxation strategy, please see: https://doi.org/10.26434/chemrxiv-2025-qnkxh.

6. For the concepts of reactivity chemistry and reactivity transduction chemistry, please see: https://doi.org/10.26434/chemrxiv-2025-wz11n.

7. For the concepts of reactivity-depleting synthesis and reactivity-propagating synthesis, please see: https://doi.org/10.26434/chemrxiv-2025-6vpc9.

8. For the concepts of reactivity speciation and reactivity adaptation speciation, please see: https://doi.org/10.26434/chemrxiv-2025-9c0bl.

9. For the concepts of site-centered reactivity and skeleton-chaperoned reactivity, please see: https://doi.org/10.26434/chemrxiv-2025-6lww1.

10. For the concepts of joint radical effect and disjoint radical effect, please see: https://doi.org/10.26434/chemrxiv-2024-ngmr5.

11. For the concept of dynamic radical effect, please see: https://doi.org/10.26434/chemrxiv-2024-sfchs.

12. For the concepts of skeleton speciation-oriented synthesis and appendage speciation-oriented synthesis, please see: https://doi.org/10.26434/chemrxiv-2024-5k9kg.

13. For the concept of molecular plastics programming, please see: https://doi.org/10.26434/chemrxiv-2023-wcr6n.

14. For the concept of dynamic polarity analysis, please see: http://doi.org/10.26434/chemrxiv-2023-cllnd.

15. For the concepts of chemistry set and set chemistry, please see: https://doi.org/10.26434/chemrxiv-2023-bg0x0.

16. For the first achievement of catalytic olefin-imine metathesis, concepts of neighboring appendage participation, homomorphic metathesis, connectivity-heteromorphic metathesis, and bonding-heteromorphic metathesis, please see: http://doi.org/10.26434/chemrxiv-2023-6jqch-v2.

17. For the concept of homeostatic catalysis, please see: http://doi.org/10.26434/chemrxiv-2022-x1cbd.

18. For the concept of relay formalism in transition metal catalysis, please see: Angewandte Chemie International Edition in English 2017, 56, 5222.

19. For the concept of reactivity relay cascade, please see: Organic Letters 2017, 19, 4359.

20. For the concept of skeleton-oriented synthesis, please see: https://doi.org/10.26434/chemrxiv.8937017.v2.

21. For the term of forward reactivity analysis and its importance for reaction discovery, please see: Chemistry-A European Journal 2014, 20, 14245; Organic Letters 2016, 18, 1178.

22. For the first synthesis of cobaltacycles under catalysis-relevant C-H activation conditions, please see: Organic Letters 2017, 19, 5348.

23. For the initial demonstration of N-nitroso-directed, transition metal-catalyzed C-H functionalization reaction (with many other reactions developed afterwards by us and other groups), please see: Journal of the American Chemical Society 2013, 135, 468.

24. For the concept of polarity relay in ring-forming reactions, please see: Organic Letters 2016, 18, 2427.

25. For the first observation of highly deliquescent property from a polymer system (with the same type of phenomenon observed afterwards by other groups), please see: Advanced Materials 2007, 19, 4548.

26. For the first observation of organogel shrinkage (with the same type of phenomenon observed afterwards by other groups), please see: Chemistry of Materials 2007, 19, 2392.

27. For the conjugate polymer with the highest metal ion detection sensitivity, please see: Macromolecules 2009, 42, 7634.

28. For the concept of monolayer-barcoded nanoparticle (with applications developed afterwards by other groups), please see: Angewandte Chemie International Edition in English 2008, 47, 5009.

29. For the initial use of fluorous tag in a detection system, please see: Angewandte Chemie International Edition in English 2009, 48, 9503.

30. For the initial use of biomineralization in a detection system, please see: Journal of the American Chemical Society 2010, 132, 6932.

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